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D.H. Welte B. Horsfield D.R. Baker (Eds.)
Petroleum
and Basin Evolution
Insights from Petroleum Geochemistry,
Geology and Basin Modeling
i Springer
Prof. Dr. Dr. h.c. Dietrich H. Welte
Institut fur Erdol und Organische Geochemie (ICG-4)
Forschungszentrum Jiilich GmbH
52425 Jiilich
Germany
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Preface
Introduction .................................. 1
Outlook .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 521
Prof. Dr. J. Rullk6tter, Institut fiir Chemie und Biologie des Meeres
(ICBM), Universitat Oldenburg, Carl-von-Ossietzky-Str. 9-11,
26111 Oldenburg, Germany
XIV List of Contributors
Prof. Dr. Dr. h.c. D.H. Welte, Institut fur Erdol und Organische
Geochemie (ICG-4), Forschungszentrum Jillich GmbH, 52425 Jillich,
Germany
Donald R. Baker
Scientific Interests
Petroleum geology and geochemistry, organic geochemistry and
sedimentologic controls on the nature and accumulation of organic
matter in sediments.
Thomas Hantschel
Scientific Interests
Theoretical physics, numerical analysis of basin evolution and pe-
troleum systems.
Personal Profiles of the Contributors and Editors XVII
Brian Horsfield
Scientific Interests
Origin and behaviour of petroleum and its precursors in geological
systems.
Bernhard M. Krooss
Scientific Interests
Transport processes in sedimentary rocks, natural gas generation,
dynamics of geologic systems.
XVIII Personal Profiles of the Contributors and Editors
Detlev Leythaeuser
Scientific Interests
Petroleum geology and geochemistry, organic geochemistry.
Ralf Littke
Scientific Interests
Petroleum geology and geochemistry, organic matter sedimentation
processes, basin modeling and the origin of organic and inorganic
gases in sedimentary basins.
Personal Profiles of the Contributors and Editors XIX
Ulrich Mann
Scientific Interests
Interdisciplinary approach to petroleum migration pathways based
on sedimentology, petrophysics, organic geochemistry and numer-
ical simulation.
Harald S. Poelchau
Scientific Interests
Quantitative geology and computer application, sedimentology,
geothermics, reservoir geology, and silicoflagellates.
xx Personal Profiles of the Contributors and Editors
Matthias Radke
Scientific Interests
Organic geochemistry, analytical chemistry, petroleum geology and
geochemistry.
Jiirgen Rullkotter
Scientific Interests
Structural and isotopic composition of molecular sedimentary or-
ganic constituents; application to ecology and climate developments
in coastal areas and the deep sea; global organic carbon cycle.
Personal Profiles of the Contributors and Editors XXI
Reinhard F. Sachsenhofer
Scientific Interests
Basin analysis including basin modeling, petroleum and coal geol-
ogy, organic petrology and geochemistry.
Rainer G. Schaefer
Scientific Interests
Organic geochemistry, petroleum geochemistry, low-molecular-
weight hydrocarbons, reaction kinetics, gas chromatography and
related analytical methods.
XXII Personal Profiles of the Contributors and Editors
Hans J. Schenk
Scientific Interests
Organic geochemistry, spectroscopy, kinetics and quantification of
organic geochemical processes.
Klaus Schwochau
Scientific Interests
Inorganic chemistry, chemistry of radioactive elements, coordina-
tion chemistry of technetium, kinetics of petroleum formation.
Personal Profiles of the Contributors and Editors XXIII
Dietrich H. Welte
Scientific Interests
Organic geochemistry, petroleum geology and geochemistry, basin
modeling and quantification of geological processes.
Bjorn P. Wygrala
Scientific Interests
Applied basin modeling, quantification and sensitivity analysis of
geologic parameters and processes in petroleum exploration.
XXIV Personal Profiles of the Contributors and Editors
M. NamIk Yalpn
Scientific Interests
Geology and organic geochemistry of fossil fuels, quantitative basin
analysis and basin modeling.
Introduction
Sedimentary basins are the sites where petroleum is formed by chemical re-
actions from sedimentary biogenic precursor material, where it is redistributed
by migration via permeable pathways, and where it is dumped and stored in
reservoir rocks or dissipated and destroyed by chemical or biochemical reac-
tions. As in a chemical reactor, the type of product formed, the processes
responsible for the formation, and the separation of the product from the
precursor or reactant mixture are constrained by a few critical parameters and
the prevailing physical and chemical conditions. The counterpart of the reactor
is the sedimentary basin, and the counterpart of the original feedstock is se-
dimentary organic matter. The chemical reaction is controlled in nature and in
the laboratory principally by the course of temperature and pressure changes.
In the laboratory the removal of the product is normally achieved by a special
plumbing system connecting the site of reaction with an appropriate storage
vessel. In nature the product removal occurs by migration out of the source
rocks and via permeable migration pathways through carrier rocks, to the place
of storage in a suitable reservoir rock.
However, there is a profound difference between nature and laboratory
conditions. Under natural conditions there are continuously changing ambient
conditions during the evolution of a sedimentary basin. As a consequence of
this the essential parameters, such as the chemical composition of the precursor
material, temperature, and pressure are also a function of basin evolution and
hence variables in space and time. By contrast, in the laboratory it is possible to
keep the ambient conditions of the reaction vessel and of its peripheral system
stable and to exert a rigorous control on the decisive parameters influencing the
reaction.
In essence the natural system, i.e., the evolving sedimentary basin and re-
levant chemical reactions and transport processes, is much more complex than
any laboratory scenario. Moreover, the interrelated chain of processes leading
to the end product "petroleum" is highly nonlinear. Therefore any predictive
interpretation, or, better, "hypothesis testing," concerning the formation and
occurrence of petroleum makes it absolutely necessary to retrace the changing
ambient conditions and to reconstruct the most important parameter fields.
The best possible choice to achieve this is "basin modeling" or "basin simu-
lation" as it has evolved over the past decade.
Chapter 1 discusses sedimentary basins and geological processes occurring
during their evolution from the point of view of basin modeling. It is obvious
that in this context the documentation of a rigorous time sequence in terms of
2 Introduction
1.1
Introduction: Integrated Basin Analysis
A sedimentary geologic basin is the result of the sum of all geologic, geo-
physical, and geochemical processes having acted on its component parts
during its entire geologic history. For the geoscientist faced with the inter-
pretation of a basin this presents an enormous puzzle since the evidence of
multiple historical events and processes is often fragmentary and has been
altered, modified, or destroyed by events of more recent age. For the scientist
trying quantitatively to model the history of the basin this means that only
forward models can be designed and applied: basin evolution consists mostly
of irreversible processes which do not lend themselves to inverse modeling
(Cross and Harbaugh 1990).
Understanding the geologic facts and data in terms of the basin history and
evolution requires background knowledge of the many processes having acted
on a basin, as well as their interactions. This can be achieved only when data
from all possible sources are integrated to arrive at a unified and consistent
picture. Data and measurements obtained from wells, exploration seismic,
remote sensing, and outcrops are used primarily to construct a model of
present-day conditions, i.e., the final result of all processes having acted on the
basin. In a second step they can be interpreted to shed light on past conditions
and events. Gaps can often be filled through integration of available data and
their geologic interpretation and interpolation.
The space-time continuum of generation, migration, and accumulation of
hydrocarbons involves many complex, dynamic, and multivariable processes
which occur during the long basin history and are part of "integrated basin
analysis" (Welte and Yalpn 1988). These processes are induced and steadily
driven by progressive changes in physical conditions (pVTX) that occur during
basin evolution. Sediments deposited at the surface under ambient conditions,
saturated with connate water, and with diverse compositions are in pro-
lInstitut fUr Erdol und Organische Geochemie (ICG-4), Forschungszentrum Jiilich GmbH,
52425 Jiilich, Germany
2Department of Geology and Geophysics, The Wiess School of Natural Sciences Rice Uni-
versity, Houston, TX 77251, USA
3 IES Gesellschaft fUr Integrierte Explorationssysteme mbH, Bastionstr. 11-19, 52428 Jiilich,
Germany
stratigraphic models are still the exception; this approach has recently been
tried by Lessenger and Cross (1995).
2. Tectonic deformation models range from simulating folding and faulting on
a smaller scale to crustal deformation on the basin scale (Jordan 1981;
Steckler and Watts 1978). These are usually deterministic forward models
(e.g., Jones and Linsser 1986) with the goal of reconstructing present-day
structural cross sections (cross section balancing) or basin profiles, but
some programs also use inverse modeling techniques (De Paor and Bradley
1988).
3. Ground water fluid flow models, especially for hydrogeology and hydro-
dynamics, are usually applied to movement of water in shallow porous
media over "human" time scales and, with few exceptions (Bethke 1989),
consider no burial and compaction or changing geometry (e.g., McDonald
and Harbaugh 1988)
4. The term "basin modeling" has acquired a meaning referring mostly to
simulating the thermal history of a basin for a given geologic and deposi-
tional history and, associated with it, the timing (and volume) of hydro-
carbon generation as well as migration and accumulation (Welte 1988;
Ungerer et al. 1990). These are generally deterministic forward models.
These types of models have somewhat different objectives and are rarely
integrated into one simulation system, mainly because coupling would be
become too difficult and CPU intensive. Some attempts have been made to
integrate ground water (type 3) models with chemical reaction models (Or-
toleva et al. 1987; Bethke et al. 1988). Another interesting suggestion (Ste-
phenson 1990) has been to combine features of basin-fill and tectonic
deformation models to control synthetic stratigraphy directly with input from
crustal evolution models.
Only the "basin model" (type 4) is addressed extensively in this chapter.
Similar to many other models, the basin model depends on a well-defined
conceptual model which is based on the integrated sum of all available geologic
data. The simulation is then performed on the discretized, numerical rep-
resentation of the conceptual model. Output of the simulation is compared
with the input and with independent calibration parameters, and if necessary
the conceptual model is adjusted or modified to lead to a better match between
simulation and calibration data.
This chapter discusses the principal fundamental processes involved in
basin evolution which affect primarily basin simulation. The main emphasis is
on the type of data needed to build the conceptual model, the common data
sources, and the considerations involved in defining and adjusting the con-
ceptual model. It follows the steps which the model builder must take from
describing the architecture or geometry of the basin, defining the physical
stratigraphy, chronology, and the physical properties of the basin-fill materials,
identifying the postdepositional processes, their timing, and their kinetics, to
finding the various temperature and maturation measures needed for cali-
brating the model and the final output of temperature history and hydrocarbon
generation. The treatment of these topics is to a large degree based on ideas
8 H.S. Poelchau et al.
and experience gained from working with the basin simulation programs PDI-
PC and PetroMod developed by IES Jillich.
1.2
The Conceptual Basin Model
over the entire cross section. Advanced finite element modeling systems are
capable of much higher and varying time (and space) resolution that can be
adjusted to local differences in geologic details. Therefore, the "conceptual
model" idea as used up to now must be refined and adjusted to the new
requirements, especially once three-dimensional modeling becomes a generally
used reality.
1.3
Definition and Classification of Basins and Their Thermal Regimes
For the purpose of modeling thermal and geologic history, basins are com-
monly classified in terms of their tectonic origin or their plate-tectonic position
(Bally and Snelson 1980; Helwig 1985). Crustal behavior is the prime cause of
basin subsidence and uplift, and determines much of the heat flow budget and
temperature history.
Using the first classification parameter, geodynamic or tectonic causes, the
two most common crustal basin models are the extensional and the flexural
basin. The extensional model first proposed by McKenzie (1978) and elabo-
rated on by Beaumont et al. (1982) is driven by the stretching and thinning of
the lithosphere with an associated heating and cooling cycle. The flexural basin
is best typified by the compressive foreland model of Jordan (1981) and
Beaumont (1981) which assumes loading of the lithosphere by overthrusting,
causing a depression in front of the thrust and an associated fore-bulge. A
variety of models also exist for intracratonic basins (Quinlan 1987). All these
models are significant mainly because they are process oriented and attempt to
predict the geometry of a sedimentary basin, the history of subsidence and
uplift, the associated stratigraphic patterns and types of lithologies (Ste-
phenson 1990), and most importantly the changes in heat flow from the crust
(McKenzie 1981).
Other subsidence mechanisms for basin formation listed by Dickinson
(1993) are lithospheric cooling, asthenospheric flow, and crustal densification
by phase change. Dickinson (1993) cautions, however, against becoming stuck
on a quasistatic basin taxonomy in which processes are inferred from basin
type. Individual basins are the result of a complex interaction of mixed pro-
cesses and are often to some extent unique. Thus, "basin type should be seen as
a function rather than a predictor of process."
Although crustal evolution and behavior is certainly a fundamental aspect of
basin development, it is often difficult to obtain adequate data to understand
just what the crustal history has been. In fact, many inferences about the lower
lithosphere and its development are taken from the sedimentary record of the
basins created in the crust. It is therefore tempting to propose using the tem-
perature distribution and history in the shallow lithosphere, established with
basin modeling and calibrated with sedimentary maturity parameters, for
testing the simulation results of deep crustal evolution and magmatic activity
(e.g., Neugebauer and Walzebuck (1987); McKenzie (1981}, etc.). In some in-
stances this may be possible and lead to better constrained crustal models. In
many cases, however, the geologic architecture and history of deep crust and
10 H.S. Poelchau et aI.
mantle is even less well definable (constrained) than that of shallow basin
models. As Wilson (1993) points out, "there is a wide range of magmatic re-
sponses to rifting of the continental lithosphere," reflecting regional variations
in the thermal state of the asthenosphere, the amount of lithospheric extension,
and preexisting crustal structures and their tectono-magmatic history.
Perhaps most interesting is the recent theoretical and modeling work on
vertical heat transport through the lower crust to the base of the sedimentary
section. As Neugebauer (1994) has shown with his simulations, dynamic-
thermal magma transport through the sub crustal lithosphere can take place
within 106 years (for viscosities of 10 22 Pals) and be emplaced in the crust-
mantle transition to correspond with seismic evidence. This plutonic transport
can bring an excess heat of 50°-200° C to the lower crust transition zone. By
contrast, porous flow velocities through the crust are estimated at 10-9 mls for
a minimum crustal permeability of 10- 16 m 2 • Under these conditions, flow
takes 5-10 m.y. through 15 km crust and shorter along fault zones. This
compares with about 30 m.y. for purely conductive transport. These effects can
cause 50-100 mW1m2 excess heat flow at the base of a sedimentary basin.
Nunn (1994) uses similar arguments to propose the possibility of free
thermal convection through micro fracture permeability in the upper crust,
beneath sedimentary basins. This rapid convective heat transport to the base of
the sediments cools the crust, causing additional, rapid, anomalous subsidence.
The convective system shuts down when the microfractures get cemented or
healed, starting a period of slow crustal warming by conduction. This process
could be cyclical. Thermal "plumes" reaching the sedimentary basin fill could
increase heat flow at the surface by 100-220 mW/m 2 • This concept is attractive
because there is evidence from fluid inclusions and other thermal indicators
pointing to short pulses of heating (Leischner 1994; Robinson and Gluyas 1992;
Poelchau and Zwach 1994).
The second parameter used in classification and characterization of basins is
the position in the plate tectonic system (Fig. 1.1). Since the theory of the
"new global tectonics" was established (Isacks et al. 1968) much research has
I
, Inlracon- I
I I
'Rift ,
,
'tinenlal , , PaSSive'
: basins ,:basin: 'margin '
,'baSins "
+ + +
+ + + +
Fig. 1.1. Plate tectonic style of different basin types and typical changes in heat flow with
evolution of a basin through plate tectonic stages. (In part modified after Stoneley 1981)
Basin Simulation and the Design of the Conceptual Basin Model 11
Table 1.1. Typical heat flow values for sedimentary basins (in mW m- 2 ). (after Allen and Allen 1990)
Mean Range
Extensional basins
Active ocean ridges and volcanoes 120 120-205
Active (syn-rift) back-arc basins 85 67-120
Active (syn-rift) rift or passive margin 80 65-110
Thermally subsiding (postrift) rift or passive margin 50 40-65
Compressional basins
Collisional foldbelt 70 40-97
Ocean trench foreland basin (foothitls~margin) 40 40-80
Fore-arc basin unrelated to arc magmatism 35 20-45
Strike-slip basins
Active strike-slip, deep lithosphere involvement 100 80-120
Active strike-slip, shallow thin-skinned (crustal) extension only 60 50-69
Basement
Precambrian shield 40 30-55
Oceanic crust (>200 Ma) 35 30-40
Approx. global average heat flow 65 60-70
accumulated on the crustal evolution at plate boundaries and within the plates.
Basins can be situated on passive or divergent margins (usually related to the
extensional type of basin), on compressive or convergent margins, or on
transform or strike-slip faults. Each of these positions show characteristic
thermal behavior (Fig. 1.1) which can be used to estimate heat flow history
associated with basin evolution (Condie 1976; McKenzie 1981). Allen and Allen
(1990) have succinctly summarized typical basin heat flow ranges in various
tectonic situations (Table 1.1).
Subsidence and uplift history can be derived from crustal models such as
that of McKenzie (1978) or Beaumont (1981). Several newer approaches and
calculations are found in the book by Beaumont and Tankard (1987). However,
these models require knowledge of crustal thickness and, in the case of ex-
tensional basins, the stretching factor (~). This means that in many cases a
thorough analysis of the stratigraphic column and sediment succession
probably gives a more accurate subsidence history than that predicted by the
theoretical models. The theoretical approach is useful, however, where ero-
sional hiatuses are difficult to estimate, and a limit on maximum burial needs
to be established. This has been shown to be applicable especially in basin-fill
modeling including lithospheric stresses and temporal stress changes (Cloe-
tingh 1992; Kooi and Cloetingh 1989). Some of these stress models can simulate
observed seismic stratigraphic sequences and erosional hiatuses on basin
flanks, and fore-bulges similar to those observed in nature.
1.3.1
Temperature and Heat Flow History
topic is treated in detail by Yals;in et al. (Chap. 2, this Vol.) and is summarized
briefly here.
Temperature, the most important variable in basin modeling, is calculated
by various simulation programs in one of two ways. Either the temperature at
depth (z) is computed from a given (or assumed) geothermal gradient and
surface temperature:
T = z·grad T + Tsurface
or from heat flow (q) at the base of the section, thermal conductivity (A) and
surface temperature:
T = q'Z/A + Tsurface.
These two approaches or philosophies are quite different, both in the way the
models are constructed and in the way the results behave. In both cases,
however, the problem consists in making numerical estimates of past condi-
tions needed as input for the modeling.
An example of the first method is presented by Tissot and Espitalie (1975)
who outlined a method for the calculation of ancient geothermal gradients. The
procedure is essentially empirical and dependent upon the availability of a
vitrinite reflectance-depth (time) profile through the basin sequence. Using the
kinetic approach developed for the simulation of petroleum generation, they
designed a similar model for the thermal maturation of vitrinite using an
iterative technique for a best fit. The second method, starting with heat flow, is
described by Yiikler et al. (1978) who took a more rigorous and process ori-
ented approach for the reconstruction of paleotemperature.
Input for the heat flow driven basin models consists of heat flow values
specified for each geologic event and each grid point. Recent values can often
be read off regional heat flow maps based on well data or surface measure-
ments. For past heat flow values the only reasonable approach consists in using
analogies of the basin to be modeled with known plate tectonic situations. For
this reason it is important to classify the basin within a plate tectonic frame-
work and use crustal evolution models to help in estimating heat flow history.
Defining and tracking the heat source can be accomplished in several ways.
One method includes, and tries to define, the lower crust as part of the heat
generation and transfer system using present observations of thermal regimes
of typical tectonic settings, and includes radiogenic heat sources as well. The
crustal evolution model is used, and defined quantitatively, to calculate the
heat flow system. The other method defines the heat flow density at an arbi-
trary depth, usually at the top of the "economic" basement or the base of the
sedimentary section of interest, and modifies the heat flow history (perhaps
using a crustal evolution model as a qualitative guide) as one of the parameters
to fit the simulation to the calibration observations. The first method is geo-
logically more attractive because it tries to include all relevant thermal pro-
cesses, but it suffers from our general ignorance of the specifics in deep crustal
structures. The second approach is more pragmatic and simple-minded in that
it does not make many assumptions about deep crustal heat sources.
Basin Simulation and the Design of the Conceptual Basin Model 13
1.4
The Filling of the Sedimentary Basin: Stratigraphy and Lithofacies
Starting with the initial stages of a basin as a crustal depression there are
transport, sedimentation, and infilling with products of erosion and reworking
(clastic sediments) and biogenic materials or chemical precipitates (mainly
carbonates and evaporites). The process of infilling of the basin is controlled by
the crustal evolution (i.e., the tectonic basin type), orogenic development of the
hinterland supplying the sediments, and the prevailing climate. Definition,
classification, or even prediction of the types of sedimentation and, where
possible, the details of sedimentary environments is one of the tasks of basin
analysis. The primary purpose of this analysis is of course to assess the oc-
currence within the basin architecture of the three types of rocks of greatest
interest for the petroleum system: hydrocarbon source rocks, porous carrier,
and reservoir rocks, and rocks of low permeability serving as seals for hy-
drocarbon accumulations or aquitards for lateral fluid movement. Of further
importance is the ability to predict lateral facies relationships as well as to
foresee the typical future development of each sedimentary facet of the basin in
terms of diagenesis, porosity development, reservoir or source rock potential.
The processes of basin filling are the essential agents that determine the final
character of the conceptual basin model used in basin simulation.
1.4.1
Chronostratigraphy: Definition of Events
System Series Stage Gradstein Harland Haq Menning Bayer COSUNA a Palmer Harland 82
(Period) (Epoch) (Age) et al. 89 et al. (1989) (1987) Computed (1983) (1983) (Cambridge)
(1994) (1990) (1987) min. error
System Series Stage Gradstein Harland Haq Menning Bayer COSUNAa Palmer Harland 82
(Period) (Epoch) (Age) et al. 89 et al. (1989) (1987) Computed (1983) (1983) (Cambridge)
(1994) (1990) (1987) min. error
since most databases contain errors and tops are rarely picked consistently.
The tools available to cull out erroneous data include structural and isopach
mapping of horizons to eliminate "bulls-eyes," cross sections to check on
correlations, and integration with depth converted seismic profiles. Modern
commercial mapping packages can be an excellent aid in automating some of
these processes such as generating various maps and producing cross sections
hung on a variety of datums.
1.4.2
Physical Stratigraphy: Definition of Layers
Wagoner et al. 1990) due to the improvements in seismic processing and data
quality. The fine details that can be worked out with these methods are nor-
mally not needed for basin modeling. However, the facies sequence concept
implied is useful for estimating lateral changes in lithology and physical
properties of the layers, i.e., for interpolation between data points (wells) and,
especially, for interpretation of seismic sections.
The basic elements of sequence stratigraphy are depositional sequences -
coherent, genetically related packets of sediments with chronostratigraphic
meaning, bounded by unconformities or paraconformities. These boundaries
are of critical significance both for the definition of the depositional sequence
itself and its relationship to the under- and overlying sequences, and also for
the geologic time missing in the sedimentary record. The geometric relation-
ships of the boundaries with the internal stratification (onlap, downlap, etc.)
reflect the evolution of the basin and the relative importance of the competing
forces of tectonic basin subsidence and global (eustatic) sea level fluctuations.
The tectonic movements of the crust can be caused either by isostatic ad-
justment to loading of sediments and overthrust plates or by thermal dis-
turbances such as expansion or contraction. Eustatic sea level changes are due
to changes of total volume of ocean water relative to total volume of ocean
basin accommodation space. The resulting sea level fluctuations usually occur
on a time scale shorter than those of isostatic adjustments and combine with
crustal subsidence and sediment filling to produce a relative sea level history.
Each depositional sequence contains a succession of systems tracts which
are identified genetically as lowstand, highstand, transgressive or shelf margin
(Posamentier and Vail 1988). Each systems tract (Brown and Fisher 1977) is in
turn a sequence of contemporaneous, linked depositional systems - an as-
semblage of depositional environments typical for each of these four types.
Lowstand tracts consist of basin floor deposits, slope fans, and continental
slope wedges. Highstand tracts include subaerial (alluvial, fluvial, deltaic) and
shelf deposits. Condensed sections are typical for transgressive tracts.
Depositional environments can be classified in terms of energy of the
transporting medium. This is quite useful because the physical properties of
the resulting sediments reflect the energy level of deposition. Transport energy
primarily influences the carrying capacity of the medium, hence the size of
particles carried, and secondly the sorting of particles. Thus, high-energy en-
vironments such as wave dominated shore lines or alluvial fans tend to pro-
duce well sorted or coarse grained deposits with better porosity and
permeability and low organic matter concentration. If porosity is preserved,
these rocks serve as carrier beds or reservoir rocks. Conversely, environments
in slowly moving or still waters are sites for accumulation of fine grained
sediments having lower permeabilities and decreased oxygenation. These tend
to have higher concentrations and better preservation of organic matter and
may become petroleum source rocks or reservoir seals.
Depositional environments have typical lithofacies associations. Such facies
models (e.g., Walker 1984) can facilitate estimation of initial (at time of de-
position) properties such as porosity, permeability, and associated parameters
as thermal conductivity and heat capacity. In addition, two other parameters
20 H.S. Poelchau et al.
1.4.3
Accumulation Rates and Subsidence: The Burial History
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, , ,
, , , , , , ,,, ,
, , , , , ,
, , ,,
3.2'10-13 , , , , , , , , ,
evapo'rite : carb. : ' , , , , prodelta: lake: fluvial
basin : shelf: ', isolated cont. clastic : ' fill of
, ,
: :
, , platform
: , rise shelf :
' slo~e'
delta
. gr~n
: re~fs : : : : : :~ : : .: pl~ln
.........-'-r-"........ _'- .. - :- - :- -:- -r --~ .. JS8B leve/t - _.. -:- -...
I :
,
I I I ._ ..J - I
, ,
I I
, I •
I I :
----~
' ..
minor or , 'I
significant
negligible
siliciclastic nput
i
-'--
,
deep sea fan siliciclastic
source
* sedimentation rate limited by subsidence
Fig. 1.2. Summary diagram of typical sedimentation rates in various depositional environ-
ments. Note that the scale is logarithmic. (Einsele 1992)
22 H.S. Poelchau et al.
supplied in large quantities and laid down rapidly or where parts of basins
were starved and only fine grained particles accumulated very slowly. Pri-
marily, sedimentation rates are important because they reflect, albeit im-
perfectly, the subsidence rates of the basin. In addition, they influence the
preservation of organic matter and quality of source rocks as discussed in
detail by Littke et al. (Chap. 5, this Vol.).
Accuracy of age dating and the use of different time scales can strongly
influence the appearance of sedimentation rate diagrams (Fig. 1.3). In the
illustrated example, assignment of new dates from the Haq et al. (1987) time
scale, to replace those of the original report by Scholle (1977), resulted in much
higher sedimentation rates in the upper Cretaceous and reduced the very high
sedimentation rates at beginning of the Cretaceous. By comparison, a burial
history diagram which plots cumulative thickness against time is less strongly
affected by errors or changes in geologic age dates. Thus, sedimentation rate
diagrams are a useful and sensitive tool to point out unreasonable age as-
signments which show up as high (or too low) apparent rates of deposition,
and which should be corrected before basin modeling.
Subsidence, that is the depth of burial changing with geologic time, can be
displayed in the form of a burial history diagram plotted as depth against age
mlm.y.
a 20 40 60 80 100 120 140 160 180
a
20
40
i 60 Scholle
Q)
~
a
~ 80
100
Fig. 1.3. Sedimentation rates of
formations in the COST B-2 well
calculated for Scholle (1977) age
120
dates and using the Haq et al.
(1987) geologic time scale. Note 3OS rnlm.y . .....
the large differences caused by the
two time scales in the upper Cre- 140 ..... iDil / M
taceous and at the base of the o 20 40 60 80 100 120 140 160 180
section mlm.y.
Basin Simulation and the Design of the Conceptual Basin Model 23
for a particular well or area. Van Hinte (1978) has popularized this concept
under the name of geohistory diagram. Burial history diagrams are useful as a
background for showing temperature history and for estimating timing of
hydrocarbon generation when vitrinite reflectance or other maturity param-
eters are overlaid on the subsidence curves. Plotting cumulative thickness of
layers against age results in a set of curves such as Fig. 1.4 which show the
subsidence and sediment accumulation through time for a particular well.
Age [Ma]
130 120 110 100 90 80 70 60 50 40 30 20 10 a
1000
2000 I.c
g-
o
3000
- present thickness
- decompacted 4000
n::n difference
Age [Ma]
130 120 110 100 90 80 70 60 50 40 30 20 10 0
~~1I0 -......;;:::t;".!;~··rl000
§:
.c
Ci
Q)
o
depth to
sediment-water
interface
Fig. 1.4a,b. Burial history diagrams (COST B-2 well). a Note the large discrepancy between
present (compacted) and decompacted thicknesses. The decompaction was calculated using
the Sclater and Christie (1980) backstripping technique as implemented in a program by
Gildner (1990). b Note the change in geometry when water depth is considered. Unit 4
(uppermost shale) is interpreted as lower slope environment in 1500 m water depth
24 H.S. Poelchau et al.
1.404
Paleogeography and Paleotemperature
Paleogeography, that is, the topography and bathymetry of the geologic basin
and its sediment source areas through geologic history, as well as paleoclimate,
are important boundary conditions of basin simulation. Although often ne-
glected for lack of available data, the importance of including paleogeography
cannot be overstated. Some of the effects on the basin history are:
- Differences in compaction history due to varying amounts of overburden
erOSIOn
- Heat flow and temperature history affected by sediment-water interface
temperatures
- Sedimentation rates as a function of elevation and erosion of hinterland
source areas
- Sediment types and grain size as a function of sediment supply and de-
positional gradients
- Recharge with meteoric waters affecting fluid flow directions and diagenetic
processes
The first two points enter directly into the basin simulation as input while
most of the other effects should be considered, at least indirectly.
It is often very difficult to obtain quantitative data on the distribution of
elevations of the paleosurfaces and on paleotemperatures. Paleontology is
probably the most common source of paleobathymetric information. The study
of microfossils has become especially useful and in some cases almost routine
for this kind of information; for example, the presence of arenaceous forams as
Basin Simulation and the Design of the Conceptual Basin Model 25
~
z
r\. // / ' "'" r......
-- 15
l/~
- 10- 20 t....... I" t-- V '-= 10 [ ;
" I\. ~ VJ I l,....-- I--""'" f' "'" 1'- f15 l~ z ~
60° ........... t--5. V V ... ....... .-
~ V If /' - r--..... 25 1\ ~ 60°
...... io"'" .......
i-"'" r--..... ........ 10 i--"" V /
- 20 ~
"'" . /~ tI\..
40° - .." ---;;,;
"-- 20 ~~ 40°
15 V
/ I - 10... / ~ - -,.:; ..-; I' -.....
"- ........ 20 ;;-- -
25 r-- /' ... ... -' ~
20°
-- -. - V- -- - - -- - - 20°
- ....... --- ",'" ...... 25 f-" 30 r---....
"- £ .... "....... '-
.~ V ~ 25
0° ... 1--- -
~
V
-~ - ~
~
r" ........
- .""r ~
V' 0°
f\.
- 25 r" r--- ..... V --
20° ,. V -..... ........
30 20°
- 25 20 r-. ~ / ........
"'-- . /
40°
- - ./ 15 "\ r--.... .... V - r-- /
40°
10 1-0... 20 I'-- .......... V , 20 V
. . .V ....t!.
-
I-
""""
l,....--' I ' V .... 5 r.....
,
\. ['.. ".......
- , ...... 25 7V
60° - ....... fO- 60°
l!i
v V 1\' ,\ 15 r--.... /'" - I~ '{ V
..... I" ," "- !.... l/
...... i"'-... r--..... r- r- 20 i.--"" , ......- r 10 III ~
§.., - / :\ 5..,
V ,~ L,....- ~ -/ 5
...... r-
90°
10 r- '" ~ goo
350 300 250 200 150 100 50
T1MEtMa "
EIIIIY - Late Early ILate I E.I Mid. I Late lJaa Maim Early LaIIIt Pal. I Eoc..e I OIkIoc.1 Mloc-.e IP.
Caibciniferous Permian- - T -TIIilaic Jul'lllllic Crelaalous Te
Basin Simulation and the Design of the Conceptual Basin Model 27
500
1000
MiddltH.ower SloptJ I Bathyal
1500
~2000
g
c.
~
<I)
Continental Rise
o 2500
Qj
<ti
~ Abyssal
3000
3500
Abyssal Plain
4000
Trench / Hadel
4500
lI<
5000
Fig. 1.6. Depth profiles of bottom water temperatures for several transects in the Northwest
Atlantic Ocean margin. (Data from Emery and Uchupi 1972; faunal zones after Berggren in
Haq and Boersma 1978)
..
Fig. 1.5. Geologic age-latitude plot of average ocean surface temperatures. (From Wygrala
1989, based on data from Frakes 1979)
28 H.S. Poelchau et al.
1.5
Postdepositional Processes
1.5.1
Compaction and the Evolution of Rock Physical Properties
Porosity
versus time and/or depth, i.e., the compaction history (Chapman 1981). De-
creasing porosities with depth can be a function of overburden thickness, time,
lithology, depositional environment, pressure development (including over-
pressuring), diagenesis, and tectonic stress (Chilingarian 1983). A wide range
of porosity-depth trends is possible, and Figs. 1.7-1.9 show examples of po-
rosity-depth trends for the basic lithotypes sand, shale, and limestone.
A multitude of factors interactively influence porosity development and
compaction (e.g., see Chilingarian 1983, p. 86ff and Table 3 for sandstones,
p. 69ff for shales), and interpretations using individual factors can be mis-
leading. The following examples are given to stress this point.
15
1 v Engelhardt, 1960
2, 3, 4 CMn9arian, 1983
5,6 Chilinganan & Wolf, 1976
5 7, 8 Stephenson, 1977
9, 10,11 FOciltbauer, 1974
12 Sian, 1983
13 Holland el aI., 1980
14 Thomson, 1982
15 Sclaler & Chrislie, 1980
16 IES
6
\ ,
14
7+---~-r-----.------.------r-----.----~
Fig. 1.7. Porosity-depth curves for sandstones from various published sources, (Wygrala
1989)
30 H.S. Poelchau et al.
--- ---
-
~ 2 Larsen & Chilingar (1983)
~ 3,4,5 Magara (1978)
a. 6 Chilingarian (1983)
eD 7 Dickinson (1953)
0
8 Proshlyakov (1960)
9 Meade (1966)
4 10 Athy (1930)
11 Hosoi (1963)
12 Hedberg (1936)
13 Magara (1968)
14 Weller (1969)
15 Ham (1966)
5 16 v.Engelhardt (1970)
17 Bryant et al. (1975)
18 Skempton (1970)
19 Fuchtbauer & Muller (1970)
20 Bjl/Jrlykke (1983)
21 Sclater & Christie (1980)
22,23 Bredehoeft et al. (1988)
6 24 Neglia (1979)
(~24 25 IES
7+-------~------~------r_------r_----~r_----_,------~
Fig. 1.8. Porosity-depth curves for shales from various published sources. (Wygrala 1989)
11
2
E
e
..c:
a.
Q)
°3
Mc Crossan (1961),
4 in Chilingarian (1983)
3 Scholle (1983)
4-10 Scholle (1977)
11 Schlanger & Douglas (1974)
12 Van der Lingen & Packham (1975)
13 Schmoker & Halley (1982)
14 Schmoker & Halley (1983)
5
15 Sclater & Christie (1980)
16 IES
Fig. 1.9. Porosity-depth curves for limestones from various published sources. (Wygrala
1989)
fluence solution and cementation processes which can negate the direct effect
of viscosities (Gregory 1977; Stephenson 1977). The general conclusion is,
however, that the effect of temperatures on porosity is negligible when com-
pared to other factors (Schopper 1982).
Diagenetic processes can either reduce or enhance porosity. Minerals in
contact with pore water are subject to chemical alteration or dissolution, de-
pending on the ion balance in rock and fluid and the temperature (and to some
degree pressure). The pore fluid may precipitate certain minerals as cement,
depending on the relative saturation of ions needed to form these cements. The
critical saturation is of course temperature dependent.
Most basin modeling systems simulate porosity change as physical com-
paction with burial but do not deal with the fact that a large amount of porosity
32 H.S. Poelchau et al.
is lost (and some also gained) through chemical diagenesis. The choices are
then to ignore the effects of diagenesis or hope that they cancel out, to adjust
the compaction or porosity/depth functions in such a way as to average in the
porosity lost due to diagenesis, or to attempt modeling of chemical reactions
coupled with fluid flow and diffusion transport as part of, or parallel to, basin
modeling.
Of the many possible diagenetic mineral reactions there are a limited
number which are volumetrically important and common enough to be en-
countered in most sandstones. They concern mostly silica or quartz, carbonate
cements, feldspar dissolution, and clay mineral reactions. Some of these are
listed in Table 1.3. Reactions can be grouped as to typical depth or tempera-
ture: shallow reactions occurring between surface and about 75° C and deeper
reactions at greater than 100° C.
Shallow diagenetic events such as kaolinite formation are often a response
to fresh (meteoric) water flowing through the sediments (Bj0rlykke et al. 1989).
Early events can strongly influence the later diagenetic evolution of a sand-
stone. Early carbonate filling of pores creates a potential for later secondary
solution porosity (McBride 1984), and chlorite rims in volcanic rich sediments
(Tillman and Almon 1979) appear to have prevented later quartz overgrowth
and porosity occlusion. In general, original differences in texture, i.e., het-
erogeneities of permeability, tend to be enhanced by diagenesis and determine
the final porosity distribution.
The type of diagenetic reactions possible and the manner of porosity de-
struction or enhancement are largely determined by the original composition
and texture of the sediment. Volcanogenic sandstones tend to develop zeolite
or iron-rich clay cements as well as early silica precipitation. Marine sands are
usually rich in biogenic carbonate particles and tend toward carbonate ce-
mentation. Arkosic (feldspar-rich) sediments give rise to pores filled with
kaolinite but may also develop good secondary porosity.
Among the deeper diagenetic events, pressure solution of quartz grains
around 100° C and the accompanying loss of porosity through pore-filling
overgrowth and additional compaction appears to be dominant and very
common, especially in the North Sea (Bj0rlykke et al. 1986) and many other
Table 1.3. List of common diagenetic reactions and their temperature ranges in sandstones.
(Bj0dykke et al. 1989)
areas, such as the Alberta Deep Basin (Zwach and Poelchau 1993). Albitization
of feldspars also has been observed in many cases (Boles 1982).
In the case of carbonate rocks, cementation starts almost immediately after
deposition (Friedman 1975), but loss of porosity continues with increasing
burial depth (Schmoker and Halley 1982). Therefore the compaction behavior
of carbonates tends to be quite different from that of siliciclastic sediments.
The conclusion here is that no single factor is sufficient to determine the
porosity-depth values and no generally valid porosity/depth functions exist
(Bj0rlykke et al. 1989); a quantitative multiparameter approach is required.
Internal factors which control porosities, for example, temperatures, fluid
viscosities, and permeabilities, are taken into account by the simulation pro-
gram but external factors such as cementation or tectonic effects can be
handled only indirectly.
rection; however, the overriding factor in fluid transport is the fluid potential
gradient, which forces flow in a generally vertical direction during burial in
spite of permeability anisotropies (Chapman 1981). Flow is usually upwards,
but occasionally downwards, for example, from compacting shales into un-
derlying, more porous units. Permeability anisotropies must be taken into
account during the simulation and fluids moved according to the pressure
gradients; this means that fluid movements from an overpressured shale unit
into underlying sands are simulated correctly.
Permeability generally decreases as a function of porosity with burial depth.
Certain sediment types, such as soils, do not adhere to this general rule (Brace
1975) and investigations of specific sites such as a reservoir or sedimentary
unit at a certain depth may not show a discernible relationship between po-
rosity and permeability (Bj0rlykke 1983). However, the relationship does exist
as basic, subparallel trends in all types of sedimentary rocks during their burial
from the surface throughout the depth range of hydrocarbon generation and
accumulation, Le., to at least 8000 m.
The porosity-permeability relationship is controlled by primary deposi-
tional factors such as grain size, distribution, shape, orientation, packing, and
surface area (Rieke and Chilingarian 1974), as well as by later secondary factors
such as fracturing, cementation, and other mineralogic processes. Functions
such as the Kozeny-Carman equation have been developed to define the re-
lationship, but the number of variables is too large to allow these general-
izations to cover all types of lithologies and burial histories. It is, however,
possible to define porosity-permeability relationships for specific lithologies
which represent an acceptable mean from the range of possible values
(Fig. 1.10). As most of the data is from reservoirs, however, it is difficult to
assess whether the available data is representative for sediments in general.
Cementation can reduce porosities in sandstones considerably without
significantly reducing permeability (Bj0rlykke 1983); however, the resulting
general trend of porosity vs. permeability in sandstones is quite well defined,
with permeabilities mostly ranging over only approximately two orders of
magnitude for any selected porosity value.
Data on shale porosity-permeability relationships are not widely available
due to the absence of perceived, direct economic importance (i.e., reservoir
analysis), due to inherent problems in measuring core samples disturbed by
drilling and to difficulties in indirect estimates in wells caused by the low
permeability values (Magara 1978). Based on studies reported in the literature
(Bryant et al. 1975; Neglia 1979) shale permeability values mostly range over 3-
4 orders of magnitude at a specific level of porosity. Permeabilities are between
1 and 10-3 mD at 70% porosity and decrease to 10-2 to less than 10-6 mD at
porosity values of 5%.
Porosity and permeability in limestones are less closely related than in the
other lithotypes due to the influence of cementation and fracturing. Complete
lack of permeability in porous limestones is a common occurrence. Poorly
defined porosity-permeability relationships in carbonates in general necessi-
tate adaptations to specific, local conditions and burial histories. An extensive
selection of permeability/porosity data is available in Schopper (1982, p. 289ff).
Basin Simulation and the Design of the Conceptual Basin Model 35
4 3 2
, I 1 IES sandstone
10 " : 2 IES sand & shale
·3-6 Chilingarian & Wolf (1975)
; 7-8 Fuchtbauer & Muller (1970)
,9 Mayuga (1970)
10 Maher (1980)
11 Holland et al (1980)
12 Withrow (1969)
-2 13-15 Curry (1977)
16 Link & Welton (1982)
-3 ·17-18 Scherer (1980)
19 Chilingarian (1983)
20 Pirson (1963)
-4 21-24 Fuchtbauer (1974)
o
Fig. 1.10. Sandstone porosity-permeability relationships from published sources. The small
circles indicate average values whereas the ellipsoids show ranges within a reservoir or se-
dimentary unit; the curves represent means for value ranges. Values affected by cementation
are also included. (Wygrala 1989)
Compaction Model
The exact determination of the rock poroSIties and their changes are very
important wherever dynamic aspects playa significant part in basin evolution.
The geometric description of basin layers and elements is directly connected
with the porosity changes of the rocks. In addition, most of the rock properties,
such as conductivity, heat capacity, density, and elastic or plastic modulus,
strongly depend on rock porosity.
Empirical or statistical average porosity-depth curves, fitted as exponential
or polynomial functions, are generally used to describe porosity changes. In
these kinematic descriptions the causes of processes (forces, potentials, loads,
36 H.S. Poelchau et al.
stresses) are not taken into account. These approximations are suitable if
steady state conditions occur, i.e., if fluids are expelled at the same rate as load
is applied. Nonsteady behavior is caused during phases of high sedimentation
rates or by material inhomogeneities (salt intrusions) or highly dynamic tec-
tonic events. This usually means that overpressure builds up because fluids are
not able to escape fast enough.
The most important assumption in these models is that the depositional
overburden load is the cause of the compaction of the lower subsiding layers.
The overburden load is responsible for the stress field in the basin. Smith
(1971) proposed to use the vertical component of the effective stress potential
as the measure for the compaction strength. The effective stress tensor cr is the
difference of the single-axis stress tensor of the external overburden load (total
stress) T and the sphere tensor of the fluid pressure (pore pressure) p acting
against the total stress. In other words, compaction is caused by that part of the
vertical overburden stress that is not balanced by the pore pressure. If the pore
pressure is close to the overburden stress, as in overpressured sediments, little
or no compaction takes place. The vertical components are identical to the
main scalar values of both p and T. The compaction law used in the simulation
can be formulated as follows:
Source
Earth's crust 2.0-2.5 Mean value range, Kappelmeyer and Haenel (1974)
Rocks 1.2-5.9 Sass et al. (1971)
Sandstones 2.5 Clark (1966)
Shales 1.1-2.1 Clark (1966), Blackwell and Steele (1989)
Limestones 2.5-3 Clark (1966), Robertson (1967)
Water 0.6 At 20 0 C
Oil 0.15 At 20 0 C
Ice 2.1 Gretener (1981)
Air 0.025 CRC (1974) Handbook
Methane 0.033 CRC (1974) Handbook
Basin Simulation and the Design of the Conceptual Basin Model 37
3.5
y 3
'E 25
~.
u 2
c
8 1.5
iii
E
!ii
5
0.5
Fig. 1.11. Thermal conductivities of selected rocks and fluids. The values for rocks are matrix
conductivities for 0% porosity at 20° C. (Data from IES 1993, Blackwell and Steele 1989; Clark
1966; Weast 1974)
38 H.S. Poelchau et al.
where f1.3 are the fractions of the components of lithology and pore fluids
(Lfi = 1.0), and A1.3 are their respective conductivities. This is similar to the
approach used by Brigaud et al. (1990).
3.5
-
,
ss + water
i'
3.0 ~
~~ -- ss + oil
c--
"'II
--
E 2.5 - ss + 50%gas r-
.............. --
'~
,~
, ~r----..
ss + gas
~
--
'ri 2.0 ...
...............
~
r::::
o
1.5
' ..
~-- r---.... t--..
"' ..... r-. ..... ~~
-- ---- -- --
1\1
E
' .... .' ......
~
,
..::..::...::. ...
1.0 --- -
I-
I-
1"-- ... ~
0.5
HSP28.2!#l
0.0
o 0.1 0.2 0.3 0.4 0.5
Porosity
Fig. 1.12. Thermal conductivity of sandstone as function of porosity and pore fluid (at
ambient T and p)
Basin Simulation and the Design of the Conceptual Basin Model 39
.:: 1:\
::: I . :',
::::r:\,
I::::1: : . ~"
<: ::c: ~\
65 65
2000 2000
'g :1:: : ~ ~
I 1~ :: 1 :::: ~\ 2:
a 1~ : t:: r~>, ~
~
~ L>:>::: ~\,
~ I ••. 1... ' ,;:', 115 115
CD
CL
E
CD 4000
I-
6000
165
Fig, 1.13, Influence of porosity, temperature, and pore-filling fluids on the effective thermal
conductivity of a sandstone. Note the large difference between sandstone filled with methane
and sandstone filled with water. Note also that thermal conductivity of gas filled sandstones
keeps increasing to much greater depth than that of water filled sandstones. (after Zwach et al.
1994)
conductivity rises almost linearly with temperature while pore water con-
ductivity levels out {Fig. 1.13}. On the other hand, when the gas saturation
increases slowly, the conductivity curve lies between the water and gas curves
and eventually joins the gas curve with an overall effect of decreasing con-
ductivity with depth.
The gas effect on thermal conductivity and temperature history was tested
with a modified code of the program package PetroMod (IES 1993) taking into
account hydrocarbon saturation changing with geologic time and differing in
space. Figure 1.14 shows the thermal insulation effect of a "gas bubble" in just
one part of the section, representing a spatially and temporally limited gas
field. The change in isotherms and maturation of the source rock is clearly
visible.
Gas fields usually have a limited extent in a basin but can still have a marked
local effect on the temperature history and distribution. This effect should not
be ignored. By contrast, some sedimentary basins, such as the Alberta Deep
Basin and the San Juan Basin, have deeply buried sections that are completely
gas saturated beneath a water-saturated zone {Berry 1959; Silver 1968; Masters
1979, 1984}. Clearly, gas saturation must be considered for the calibration of
the basin thermal history with the consequence that input parameters such as
heat flow would have to be lowered in order to match measured vitrinite
reflectance. Studies in the Alberta Deep Basin {Zwach et al. 1994} have shown
Basin Simulation and the Design of the Conceptual Basin Model 41
---
depth
--- --
grid points
o
,7--=---. .... - -.... m
.- -
11J"- - ~- ~
, '----
4Oo¥ __ - - - - - - ,-
---
- 40;
____ .i- __
, ---.....-..- - - -I
1000 .....- -""'""
-
m
- --
, ...- .....t-=-
,
~-'
- - -- - .... 3
sediment
-
...J .\- ...J
2000 layers
---
m
.... -... -
-- - -
-160·C
--- ...
- -, - 3000
m
Fig. 1.14. Simulation of a schematic hydrocarbon trap comparing the effects of water and gas
saturation on temperature. Left, All sediments water filled; right, gas filling in structurally high
position of layer 6. Thin lines, layer boundaries in a sand-shale sequence; dashed lines,
isotherms showing the simulated present-day temperature field. Gas was generated in layer 1
and has migrated upward into a sandstone reservoir (layer 6) beneath a shale cap rock (layer
7). Gas saturation in the trap was assumed to be present for the past 20 m.y. (Zwach et al.
1994)
how different the reconstructed heat flow history can be when gas is partially
or completely substituted for water as pore-filling fluid. Conversely, comparing
water and gas filled models for the same heat flow history demonstrates greatly
increased vitrinite reflectance and much higher petroleum generation.
1.5.2
Erosion of Overburden and the Estimation of Maximum Burial
:;,
Calberlah _ ~0 __
~ _I.~
-~-
500
Dannenbiittel ~ ~~o...:::::::-
_
10~' ~
=
.....
1000 : i _ -~-
. ,§'-
.
'8 ~-
Cii ~-
gj ~-
t::;'-
Gl
.... 1500
oS ~
.c
Q.
=
i'0
~2000 ~
2500
3000
HSP4.3.96
3500
0 5 10 15 20 25 30
Shale Porosity [0/0]
Fig. 1.15. Typical curve for sonic travel time (.M) and porosity vs depth for Lias epsilon
(Jurassic) shales at maximum burial depth; this figure illustrates method (1) for estimating
thickness of eroded overburden. Data from Gifhorn Trough, northwestern Germany. (Jan-
kowsky 1962)
Basin Simulation and the Design of the Conceptual Basin Model 43
r
~.
/
i
o
1
~
500 (},o~ !
'/.
i
~Vo
o~ i
1000
~'
i
I
%1500 a 0
0(1
0
00
c3 '"" carcJiumSs
' 0';
/8' :
2000
8§
i
0
a
2500 0
i
o§ c9 i
a 0 :
3000 HSP6.7.1<'
Fig. 1.16. Estimate of erosion of overburden in a well based on extrapolation of sonic interval
transit times vs depth to an uncompacted shale value of 656 !ls/m; example for method (2)
decribed in text. Data from Western Canadian Sedimentary Basin (Alberta). (Reprinted from
Magara K., Geological models of petroleum entrapment, 1986, pp 1-328, with kind permission
from Elsevier Science - NL, Sara Burgerhartstraat 25, 1055 KV Amsterdam, The Netherlands)
and no data exist, for construction of a standard burial curve (Poelchau and
Zwach 1994). First, the amount of erosion was estimated with the extrapolation
technique (2) for several wells widely distributed over the study area. These
points were used to calculate maximum depth of burial for one of the younger
shale formations for which average I1t values could be determined from the
sonic logs, and then fitted to Magara's (1986) model:
z = A·ln(M - I1t m ) + B
This is equivalent to the standard burial curve (1) and allows calculation of
maximum depth of burial for this shale layer in all wells having sonic logs in
44 H.S. Poelchau et al.
the study area and, by extension, permits mapping of the thickness of over-
burden removed by erosion.
Maturation of organic matter, i.e., vitrinite reflectance (VR), has been used
in analogous ways. Connolly (1989) has estimated erosion by extrapolating
log VR trends to a surface value of 0.2%. This approach is based on earlier
attempts by Hacquebard (1977) who used coal rank and moisture to determine
the maximum burial of Mannville coals in Alberta. Weiss (1985) has used a
more refined approach (Fig. 1.17). Matching measured vitrinite reflectance to
vitrinite reflectance calculated via the time-temperature index (TTl; Waples
1980) for various overburden and temperature gradients, he established groups
of curves for several shales and estimated the most likely temperature gradients
and overburden for several wells in Alberta.
Use of vitrinite reflection for estimation of overburden or erosion is rela-
tively easy where data are available but has two distinct disadvantages. The
extrapolation approach assumes that only the temperature associated with the
maximum burial depth has influenced the maturation. Clearly this is not al-
ways the case since points at different depth may have resided at these tem-
peratures for varying lengths of time. Secondly, since vitrinite reflectance is
commonly used for calibrating the basin simulation temperature history, it
should be reserved for that purpose and not, even indirectly, enter the input
data for the simulation.
4 321
35
IWell 10-19-70-12W6 I
30
E
~ 27
()
~ 25
C
Ql
15
III
(5
(ij 20
E
Q; Error bars ~ ± 0.1 %R m
.I:; 1 Petrel Member
'0
Ql
2 Base 01 Fish Scales
(!) 3 Falher ( Fourth Coal )
4 Base 01 Cadomln
15
Fig. 1.17. Calculated thickness of eroded overburden in several formations for various as-
sumed geothermal gradients. The values plotted are the result of iteratively calculating the
vitrinite reflectance from TTl with varying overburden until they match the measured vitrinite
reflectance. (Weiss 1985)
Basin Simulation and the Design of the Conceptual Basin Model 45
1.5.3
Methods of Predicting Diagenesis
the two types of processes with more or less simultaneous solutions. Several
studies have made inroads to model at least a simplified system, either by
limiting the number of reactions (Ondrak 1992), solving only for one dimension
and constant temperature (Lichtner 1988) or working with only a few cells or
limited time steps (Ortoleva et al. 1987). These models can, for fairly specific
and simplified conditions, provide possible scenarios which can be checked
against observations. Thus certain hypotheses may be ruled out or accepted.
Zwach and Poelchau (1993) provided an example of the way in which
petrography, basin modeling, and diagenesis modeling can be integrated. In a
study of the Albian Cadotte Sandstone of the Alberta Deep Basin in Canada,
basin modeling provided temperature, pressure, and porosity data as well as
the structural geometry of a cross section of the sandstone at the time of
deepest subsidence (48 Ma). These data were used as input to a coupled flow
and chemical reaction model developed by Ondrak (1992). Simulating the
amount of quartz overgrowth due to regional flow of cooling pore water which
might occlude the remaining porosity produced results that essentially re-
pudiated the hypothesis of regional flow cementation. Instead, Zwach and
Poelchau (1993) postulated from petrographic observations that pressure so-
lution of chert grains provided most of the silica cement found on quartz
grains. This supported the alternative hypothesis that small scale, closed sys-
tem processes had affected the porosity much more than regional flow.
In general, whether a system is open or closed and the scale on which pore
fluid transport affects diagenesis is still a major question. Bj0rlykke has re-
peatedly published evidence (e.g., Bj0rlykke et al. 1988) that most deep diag-
enesis is an isochemical process in a closed system with little long range
transport. The exception is meteoric water advective transport which normally
takes place early in shallow rocks (Nedkvitne and Bj0rlykke 1992). In many
cases, such as quartz pressure solution and overgrowth, the main transport
process appears to be very small scale intergrain diffusion, requiring no ad-
vective transport at all but still accomplishing major porosity changes (Zwach
1995).
1.5.4
Structural Deformation History
Growth Faulting
temperatures and salinities, but also potential gradients and flow directions can
provide clear evidence for faults acting either as seals or as conduits on a local
as well as on a regional scale. Indications are that faults can be both seals and
conduits, and that flow can occur periodically along faults which are otherwise
sealed, especially during phases of increased fault activity (seismic pumping).
Many examples of growth fault systems with well-documented measured
data have been published, especially in the Gulf of Mexico (e.g., Flemings et al.
1992), which conclusively prove the existence of fault-induced perturbations of
pressure and temperature fields in an abnormally pressured environment.
However, resolution generally does not suffice to determine whether the fault
or fault zone is open, providing a path for fluid movement and the concomitant
perturbations, or whether it is acting as a seal and therefore forcing fluids to
ascend in front of the fault zone.
Overthrusting
plane angles, thrust sheet movement rates, and erosion during overthrusting as
well as the role of thermal conductivity and heat capacity of the lithologies. The
study showed that one-dimensional instantaneous emplacement concepts
oversimplify the actual processes as equilibration occurs mostly during the
time of thrust sheet emplacement, and that disequilibrium, or temperature
inversion, occurs only when thick sheets (approx. 4+ km) are emplaced with
high movement rates (approx. 5 cm/year; Fig. 1.18). The sawtooth-shaped
temperature profile of Oxburgh and Turcotte (1974) cannot be generated under
realistic geologic conditions. The total amount of heat transported in the thrust
sheet itself (by convective or mass transport) is negligible compared to the total
amount of heat flowing through the sequence from the basement during the
overthrusting process.
The implications for hydrocarbon generation are that there are no simple
solutions due to the number of the variables which must be taken into account
or at least subjected to a sensitivity analysis. One-dimensional "short-cuts," for
example by simply "depositing" a thrust sheet with high sedimentation rates,
can be misleading. One-dimensional simulations, though mathematically cor-
rect, only permit an approximation of temperature histories in thrustbelts,
even if the results may be sufficiently accurate in some cases to provide a
qualitative calibration and interpretation of thermal histories.
Salt Movement
The thermal effects of salt movements are another case where generalizations
are common, but where the problems are often oversimplified, leading to in-
accurate or even erroneous conclusions. The most widespread generalization
on the thermal effects of salt bodies is that they act as conductive "pipes" due
to their relatively higher thermal conductivities and lower porosities. There-
fore, temperatures in a salt dome are higher than in the adjacent rocks at any
given depth level. However, Lewis and Rose (1970), using a simple model, show
clearly that thermal conditions in and around highly conductive bodies can
vary depending on the type and geometry of the structure as well as on the
depth level relative to the structure at which the temperature or the heat flow
values are being compared. Both temperature and heat flow distributions are
perturbed. Near the base of an isolated highly conductive body temperatures
are lower than in the adjacent rocks, while near the middle level of the body
there are no lateral temperature differences, and near the top of the body
temperatures are higher within the dome than in the adjacent rocks. These
conclusions are made for a completely buried dome and additional complex-
ities ("cold" vs. "hot" domes) arise when a dome has penetrated the entire
overlying sedimentary sequence to reach the surface.
Simple models with uniform heat flow values at a sufficient depth below the
base of the highly conductive salt dome, show that heat flow values within the
dome (i.e., from below the base to above the top) are higher than in the
adjacent rocks, but in the immediate lateral vicinity of the dome there is a zone
where heat flow is even lower than in the surrounding rocks at greater dis-
50 H.S. Poelchau et al.
~ rapid overthrusting
Gridpoints: 5 10 15 20 25
~ 4
8
HORIZONTAL SCALE
2km
10
~ rapid overthrusting
Gridpoints: 5 10 15 20 25
20
--------- ----.8'9-
------- - - ----- ------- ~ -----
2 ~ - - - - - - - - - 60· - _____ _
- - - - - - - - - - 70· - - - - - __ &0. - -
_5.. - - - - - - - - 80 ___ _
.... - - - - - - - - - 90 - - _ _ __ _ _ _10 · --'''-'-_-,:;-;o_c....:-c.:-=-.-_-_-_-_-_-_Tc.:4--t
~
-r---- - --- -- - .-;i~~~-:~-~~::~_~~:::::~:-__ ~ ~ ~ :: _\~o~,..·-~-=-"--...::;_..:;--=----------=--:-"'~2- : I-
-3- - - - - - - - ·'00- - -... ... --.. ... ... eO .... - ... - - - - - - - 1-
4
.!:
0..
c3 6
' " 140 ... _ ...... - _
.......... -
.... - ... ... ...... _
"'- ......... -.... --_ ... ..,. " \7,.1;::'
' " , . . , . ")~,,,,
\
, \~
>:> '
....... -
8
HORIZONTAL SCALE
2km
10
Fig. 1.18. Simulation of heat distribution compared for rapid overthrusting (left) and slow
overthrusting (right). Upper panels, temperature distribution at the end of thrust movement
(rapid emplacement is accomplished in 100,000 years, slow in 1 m .y.). Lower panels, progress
of temperature equilibration 1 m.y. later. (Wygrala et al. 1990)
Basin Simulation and the Design of the Conceptual Basin Model 51
slow overthrusting
Gridpoints: 5 10 15 20 25
O~--~--~~----~~----~----~----~----~------~
10 20
.--..
~ 4
- - -- .. _-- -
8
HORIZONTAL SCALE
2km --·60--· lsotherms (0C)
10
slow overthrusting
Gridpoints: 5 10 15 20 25
O~~~--~~----~~----~--~~----~----~~----~
10 20
s::.
0..
~ 6
8
HORIZONTAL SCALE
2km - _. 60 - - . Isotherms (0C)
10
tances. Then, at a sufficient distance above the top of the submerged, highly
conductive body, heat flow values can once again be uniform.
The implications of these temperature and heat flow perturbation patterns
can be considerable, for example, when thermal and hydrocarbon generation
histories are being simulated in the vicinity of salt domes. One-dimensional
models are frequently corrected only by arbitrarily increasing heat flow values
(or "temperature gradients"), and the "calibrated" values are then used for
hydrocarbon generation modeling. The simple examples above show, however,
that heat flow values are often reduced near salt domes. Factors to be taken
into account include the timing and the changing geometry of salt movement
as well as the distance of the simulated well from the salt body. Two-dimen-
sional models are a definite improvement if they can take lateral effects into
account, and if the modeled section cuts across a salt wall, but the typical
dome-shaped geometry of salt bodies necessitates three-dimensional modeling
for more accurate thermal history analysis.
1.5.5
Petroleum Generation and Estimation of Petroleum Yield
One of the ultimate goals in basin modeling is to assess the amount of pe-
troleum that could have been generated in a petroleum system from source
rocks and accumulated in reservoirs. The principal limit to petroleum abun-
dance in every petroleum system is the ability of the source rock to provide a
sufficient charge to associated carrier beds. Without adequate generation, there
can be no accumulation of petroleum no matter how favorable reservoir
quality, sealing and trapping are.
Source rocks situated within the diagenesis zone of maturation (vitrinite
reflectance <0.5%; see Radke et al., this Vol.) are usually immature. The sub-
sequent breakdown of kerogen in the zone of catagenesis (vitrinite re-
flectance = 0.5-2.0%) to yield petroleum can be discerned by a significant and
accelerated increase in the relative concentrations of extractable hydrocarbon
relative to total organic carbon. This phenomenon has been observed in the
Los Angeles and Ventura Basins (Philippi 1965), the Paris Basin (Tissot and
Pelet 1971), the Uinta Basin (Tissot et al. 1987b), in German coals of increasing
rank (Leythaeuser and Welte 1969) and many other locations. The oil gen-
eration process results in a 4- to 12-fold increase in hydrocarbon/organic
carbon ratios (Philippi 1965; Magoon and Claypool 1983; and many other
studies).
Generated petroleum-like compounds are thought to result from a multi-
tude of quasi-irreversible, assumed first-order thermal cracking reactions
(Huck and Karweil 1955; Hanbaba and Jiintgen 1969; Tissot 1969) whose
overall rate is mainly governed by kerogen structure and the extent of thermal
stress over geologic time (see also Schenk et al., Chap. 4, this Vol.). The pro-
gressive loss of components from marine kerogens proceeds according to bond
strengths with weaker bonds breaking before stronger ones, leaving behind a
hydrogen-depleted residue. Kerogen at an optimum stage of liquid hydro-
carbon generation is said to be mature. The early and middle part of cata-
Basin Simulation and the Design of the Conceptual Basin Model 53
1.6
Optimization and Calibration: Testing and Evaluation of the Model
abilities, pressure and overpressure all are recalculated at each time step and
can be graphically displayed against time or depth.
Graphic comparison of calculated values with the measured observations
quickly indicates whether the conceptual model matches the geologic reality. If
the match is good, the geologic assumptions made for the conceptual model
can be said to be reasonable although not necessarily true. If the match is poor
it can be concluded that the hypothesis of the conceptual model is false, i.e.,
that certain assumptions need to be changed. Assumptions to be changed are
usually those that cannot be measured or calculated directly or accurately.
They may include past water depth and sediment surface temperature, heat
flow, thermal conductivities, or other physical properties of average lithologies,
amount and duration of erosion, or length of an hiatus.
The systematic testing and evaluation of results, i.e., solutions and outputs,
is a crucial and distinctive step of all well designed modeling studies. Although
there is some confusion in terminology, the procedures are commonly referred
to as optimization, calibration, checking, and sensitivity analysis (Yiikler 1979;
Wygrala 1989; Hermanrud 1993).
Checking, a term applied by Yiikler (1987), refers simply to the direct
comparison of modeled solutions to comparable observational data. Dif-
ferences between calculated and observed values provide a basis for esti-
mation of probable errors in simulated outputs. When calculated outputs
are within "acceptable" error limits (which of course must be specified) of
observed values, the solution is judged as "successful" (see Welte and
Yiikler 1981).
If results are beyond acceptable error limits, the model is deemed un-
successful, and optimization procedures must be applied. This is a most critical
and significant part of the testing and evaluation of numerical modeling pro-
cedures. Specifically, optimization involves the changing or adjustment of in-
put data, pertaining both to the geologic conceptual model and the simulation
equations, followed by recalculation of new solutions which are again checked
against observational data. This is a "trial and error" procedure, typically
involving successive trials of different inputs, until acceptable solutions are
obtained, i.e., outputs of calculated results agree within the acceptable error
limits with observed values. Thus, optimization of the model searches for a set
of inputs which yield results that best satisfy or coincide with available ob-
servational data. Analogous to riflery, optimization has logically also been
called "calibration," because the procedure involves making corrections (e.g.,
adjusting sights for range and elevation inputs) so that the target (measured
observational data) is directly "hit" by the shot (i.e., output values)!
Calibration is always limited by the availability of measured observational
data. Because of its substantial influence on most aspects of basin modeling,
calibration of thermal history outputs is always essential. This is usually ac-
complished by the comparison of calculated present-time temperature profiles
and calculated vitrinite reflectance, compared to present-day measured bore-
hole temperatures and observed vitrinite reflectance-values.
Basin Simulation and the Design of the Conceptual Basin Model 55
1.6.1
Temperature Calibration
Temperature data are the most easily available data for calibration, albeit
usually restricted to present time. The most commonly used temperature
parameters are present-day bottom hole temperatures (BHT) and borehole
temperature logs.
BHT temperatures should be corrected for circulation of cooler drilling or
completion fluids. This is carried out with the Horner plot extrapolation when
two or more temperatures measured during different logging runs are available
from the same depth at different times after circulation has stopped (example,
Fig. 1.19). Because of the difficulty of correcting BHTs to steady-state tem-
perature they tend to be lower than actual formation temperature but are rarely
too high.
A similar kind of data are temperatures from drill stem tests (DST) or
formation tester (FT). They usually have been corrected already by the Horner
plot technique and often are available together with corrected formation
pressures.
Temperature logs can be a source of good temperature data if they have
been run after the well has been shut in for a sufficiently long time (weeks or
months) to reach a state near equilibrium. In some countries (e.g., Russia) this
seems to be done routinely, while in other areas (e.g., North America) this is
usually not the case. Such temperature data are usually close to real formation
temperatures but tend to be lower than DST extrapolated temperatures in the
lower part of the well and higher in the upper part.
·. . . . . ·· . ·. . . . ·(.· · · ........·. ·. r- . ·. . ·· . ·.
:
r. . ·. ·. .
:
68 ~
E
Fig. 1.19. Example of Horner Plot extrapolation method to correct BHT for cooling during
drilling and circulation. The corrected steady state temperature for this formation is 79° C
56 H.S. Poelchau et al.
1.6.2
Vitrinite Reflectance Kinetics and Other Organic Calibration Parameters
Vitrinite reflectance is the most widely used parameter to indicate the maturity
of the source rock. Since it is almost routinely measured and abundantly
available, it is also the primary calibration parameter for modeling the tem-
perature history.
For calibration, the increase in vitrinite reflectance is simulated in the basin
modeling program in accordance with the conceptual model and the tem-
perature history. Several "kinetic" models for vitrinite reflectance evolution
have been designed and used extensively. The oldest and most widely used was
Lopatin's model (Lopatin 1971), popularized as TTl index by Waples (1980).
This rather simple model is based on the premise of "dark room" kinetics that
the reaction rate doubles with each 10° C increase in temperature. The method
is simple and easy to apply but does not give proper results for basins with very
low or high heating rates (Quigley et al. 1988).
Reaction kinetic models using the Arrhenius equation (see Schenk et aI., this
Vol.) and a distribution of activation energies have been more successful. The
two models used predominantly have been proposed by Larter (1988); Larter
(1989) and by Burnham and Sweeney (1989) and Sweeney and Burnham
(1990). The Larter model is based on the observed reduction of phenolic
moieties during the maturation of vitrinite and shows good matches in the
reflectance range of 0.45 to 1.5%. The Burnham/Sweeney model describes the
chemical changes in vitrinite with four overlapping reactions: the successive
release of water, CO 2, higher hydrocarbons and methane. The decrease in these
components results in a reduction of the H/C ratio in vitrinite which can be
Basin Simulation and the Design of the Conceptual Basin Model 57
correlated with the increase in reflectance (Leischner 1994). The four reactions
are each described by an activation energy distribution in the spectrum from
38 to 74 kcal/mol and a constant frequency factor of 1013 S-I. A simplified, but
nevertheless equally effective model, the so called EASY%Ro model (Sweeney
and Burnham 1990), combines the four reactions into one spectrum of acti-
vation energies. This model has been most successful for calibration purposes
because it is applicable for maturation values as high as 4.6% vitrinite re-
flectance.
Although vitrinite reflectance is the most commonly available and routinely
measured maturation parameter used for calibration, it is not always the best.
In some situations vitrinite reflectance may be suppressed by weathering, bi-
tumen retention, or microbial alteration. In oxic environments (e.g., carbon-
ates) vitrinite reflectance can be too high. Also, there are some lithologies in
which vitrinites are rare or absent. In these cases other organic parameters can
be used instead (see Radke et aI., this Vol., for details). Leischner (1994) has
studied and compared a large number of these parameters and also con-
strained them with inorganic, diagenetic measures.
Pyrolysis (RockEval) Tmax values are an alternative maturation parameter
that has been correlated with vitrinite reflectance, especially for type III
kerogen (Espitalie et al. 1984). Provided that the vitrinite reflectance values
based on Tmax fall within the established trend, they can be used as an addi-
tional constraint. Sweeney (1990) has published a program for simulating Tmax
evolution with temperature history as result of petroleum generation, that can
also be used for further calibration.
Another group of organic maturation parameters is based on the iso-
merization and aromatization of certain organic compounds in the kerogen.
One such commonly applied parameter is the Methylphenantrene Index or
MPI (Radke and Welte 1983) which has been correlated with vitrinite re-
flectance.
Hopane or sterane isomerization is sometimes applied as additional ma-
turation calibration parameter. The kinetic reactions have been worked out by
Rullkotter and Marzi (1988) and Mackenzie and McKenzie (1983) and can be
used directly in the simulation eliminating the need for recalculation into
vitrinite reflectance.
1.6.3
Clay Kinetics as Temperature History Indicator
The transformation of smectite to illite (SII) has been known to take place over
a range of depths suggesting a kinetic process involving temperature as well as
time (Hower et al. 1976; Burst 1969, etc). Both experimental and subsurface
data involving different heating rates have been interpreted to reflect a first
order kinetic reaction, and kinetic models have been fitted to these observa-
tions (Eberl and Hower 1976; Pytte and Reynolds 1989).
Vasseur and Velde (1993) have recently developed a computer model to
devolve SI1 transformation curves and have suggested a two step model in-
volving two sequential processes and sets of kinetic parameters. This theory
58 H.S. Poelchau et al.
has been based on data from numerous different basins and settings. Each of
these settings resulted in different numerical values for activation energy (Ea)
and frequency factor (A). However, when plotted on an A vs. Ea diagram all
values fall almost on a straight line. This means that mathematically the
magnitude of the two parameters is less important than their ratio, although
chemically some of these values may be meaningless.
In practice then it is possible to find parameters for a kinetic equation that
models clay transformation satisfactorily to a given temperature history. This
model can then be used to provide an additional calibration of the temperature
history of a basin. SII transformation can be especially useful because the depths
of most rapid change are usually somewhat shallower than those of the vitrinite
transformation. For deeper sediments the process of crystallinity increase of
illite with temperature can be used as an additional calibration technique.
1.6.4
Compaction or Porosity Optimization
1.6.5
Sensitivity Analysis
ysis. This method simply involves making finite changes of input parameters
(ordinarily one at a time) for the previously optimized «successful" model
followed by recomputation of results. Sensitivity is defined as the rate of
change of the resulting output with respect to change of the input parameter
(Zwach 1995). For example, the influence of changes in the magnitude of an
assumed basement heat flow on the calculated temperature history and on
successively simulated compaction and hydrocarbon generation outputs can
be evaluated by systematically changing heat flow inputs and doing iterative
computations. Further, the effect of variations in kinetic parameters (e.g., ac-
tivation energies and prexponential factors) on hydrocarbon generation cal-
culations is commonly evaluated. In principle, the relative influence and
importance of any input parameter in governing the nature of a particular
output result for the model can be evaluated.
As one might expect, sensitivity analysis also plays an important role during
the optimization procedures. Specifically, a knowledge of the sensitivity of
outputs to variations in the magnitude of input parameters guides the modeler
in making appropriate modifications to the model. In particular, when coupled
with information on the probable natural range and inherent errors, i.e., un-
certainty in the magnitude of input parameters, optimization of the model can
be accomplished in a more realistic and quantitative fashion. Similarly, once a
«successful" model has been designated, again using expected ranges and er-
rors of input data, sensitivity analysis is used to estimate probable error, i.e.,
uncertainty, in the simulation results. An excellent example of the use of
sensitivity analysis is given by Zwach (1995) who tested the effect of change of
a whole series of input parameters (event resolution, heat flow variation and
timing, length of erosional hiatus, thickness of eroded overburden, surface
temperature, and gas saturation) on simulated vitrinite reflectance.
1.6.6
The End Result
1.7
Conclusion: A Note of Caution and Outlook
the use of systems tract and seismic facies analysis, and, finally, build an input
file for the actual basin modeling. Some versions of such input modules exist
already but need to be improved to make model building easier and faster.
Another new development is the inclusion in the simulation of processes
that are not due to the normal mechanical compaction. For instance, specific
diagenetic processes influencing porosity development, or igneous intrusions
affecting the temperature history and maturation can be used as options to make
the simulation fit the geologic reality. Similarly, the inclusion of gas saturation to
calculate lowered thermal conductivity has recently been made possible. Other,
more specialized processes will certainly be included in the future.
The main trend now is toward real three-dimensional modeling systems.
These will have to be coupled with those other types of models mentioned in
the beginning: basin-fill simulation to help build the three-dimensional stra-
tigraphy, and tectonic and structural deformation models to construct the
various stages of deformation of the basin with geologic time. This is essential
to trace the changing paths of fluid movement and heat distribution with time.
The main difficulty to overcome, however, will not be the programming, the
numerical techniques or even the high computer run time and storage re-
quirements, but the acquisition of input data to fill the elements of the basin
matrix with geologic and physical properties that should reflect the geologic
reality. But once this is achieved, this integrated, interactive kind of basin
modeling can bring the petroleum systems approach to life.
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Basin Simulation and the Design of the Conceptual Basin Model 69
2.1
Introduction
2.2
Fundamental Concepts of Heat Transfer
2.3
Heat Transfer Equation
The differential equation given by Carslaw and Jaeger (1959) allows the
treatment of heat transfer in a homogeneous and isotropic solid under steady-
state conditions and with thermal conductivity independent of temperature:
Thermal History of Sedimentary Basins 77
where T = temperature and x, y, and z are the coordinates. Equation 2.4 in-
dicates that heat is neither acquired nor lost in the any given unit volume. For
transient conditions the differential Eq. (2.4) must be extended to:
axa( Kx aT)
ax + 8ya( Ky aT) a( aT)
By + az Kz az = pc
aT
at (2.5)
(2.7)
and:
(2.8)
where, Vx, Vy' Vz are the velocity of water, Pw the density of water, and Cw the
specific heat of water.
The conductive and convective terms of the heat transfer equation were
combined by Stallman (1963) to determine the flow velocities of groundwaters:
a aT a aT a aT
ax Ks ax + 8y Ks By + az Ks az
aT
-cwPw (Vx ax + Vy By + Vz Dz
aT aT) = csPs
aT
at ± R (2.9)
the density of water, respectively; T is the temperature, Vx' Vy , Vz are the flow
velocities in directions x, y, Z; and R is a source/sink term, which can be used,
for example, for the heat input by radiogenic heat generation.
As shown by Sharp and Domenico (1976); Yuekler et al. (1978); Welte and
Yuekler (1981), Stallman's equation can handle the heat transfer adequately.
All of the physical parameters of the heat flow equation are temperature and
pressure dependent. Hence these dependencies must be taken into account
when temperature changes are to be calculated precisely.
2.4
Heat Transfer in Sedimentary Basins
2.4.1
Heat Transfer in Sedimentary Basins by Conduction
Heat conduction takes place as a diffuse process by which the kinetic energy is
transferred by interatomic or intermolecular collision in a medium where a
temperature disequilibrium exists. The amount of heat transmitted by con-
duction is proportional to the temperature gradient and to the proportionality
factor, thermal conductivity, as given in Eq. (2.1). Consequently an accurate
treatment of heat conduction in sedimentary basins requires first an appro-
priate definition of the thermophysical parameters of the sedimentary fill. This
definition must consider both spatial and temporal variations. Spatial varia-
tions are due to lithology, porosity, and temperature; temporal variations are
due to the changes in porosity and temperature caused by burial and com-
paction. Since conduction is the dominant heat transfer mechanism in sedi-
Thermal History of Sedimentary Basins 79
Sedimentary rocks are porous, and pores are usually filled with formation
fluids. Consequently, for the thermal conductivity determination of sediments
a mixed material of at least two components, namely matrix and pore fill must
be considered. Matrix is generally polymineralic and in certain cases the pore
fill is also a mixture of oil and water, water and gas or all of them. Pore fluids
playa crucial role for the so-called "bulk thermal conductivity" or "effective
thermal conductivity", because pore fluids have a remarkably low thermal
conductivity compared to matrix minerals. The thermal conductivity of sedi-
ments can be predicted if the lithology and pore filling fluid or gas are known.
The empirical relation given in (2.10) can be used for the determination of bulk
conductivities:
(2.10)
where, Ks , Kr> and Kw are the thermal conductivities of sediment, grain (ma-
trix) and water, respectively, and cjJ is the porosity of the sediment. However,
Eq. (2.10) is valid only if Kw/Kr is neither very small nor very large (Palciauskas
1986; Ungerer et al. 1990).
The effective medium theory, which enables the prediction of properties of a
composite material if the volume fractions of the individual components and
their properties are known, can also be used for the definition of sediment
thermal conductivities (Palciauskas 1986). The basic result of the theory is:
L 3Vi(2Ks + Kif
n
K;l = 1 (2.11)
i=l
where, Ks is the sediment thermal conductivity, Kj is the conductivities of
individual components, and Vi is the volume fractions. This theory is based on
the assumption that the composite material is homogeneous and isotropic,
which can be justified if volume is sufficiently larger than the grain size. Since
the volume of sediments and the size of grains in a basin fullfil this condition,
this rule is valid for sediments (Kappelmeyer and Haenel 1974).
Allen and Allen (1990, p. 287) compared the approaches for conductivity
prediction for a mixture of quartz and water in which quartz occupies 70% of
sediment volume and water 30%. Thermal conductivities of quartz and water
were taken as 13 and 1.7 meal cm- 2 S-l Gel, at T = 100°C, respectively. The
bulk conductivities were predicted as 7 and 8 meal cm- 2 S-l °e\ with Eqs.
(2.10) and (2.11), respectively.
Most sedimentary rocks are anisotropic in terms of thermal conductivity
(Gretener 1981). However, the effect of this difference is negligible, as only a
minor amount of heat is conducted horizontally due to the absence of sig-
nificant lateral thermal gradients.
80 M.N. Yalpn et al.
Morin and Silva (1984) investigated effects of high pressure and high
temperature on thermal conductivity of sediments and found that the de-
pendency on pressure is negligible. However, there is an obvious dependency
on temperature. In general thermal conductivity decreases with increasing
temperature; the effect is less for lithologies with low to moderate thermal
conductivities and greater for well conducting lithotypes, such as quartzite, and
salt (Kappelmeyer and Haenel 1974). Hence, a correction of conductivity va-
lues is necessary for sediments at greater depths.
The dependency of thermal conductivities upon porosity is much more
important for the calculation of heat transfer in sedimentary basins because the
changes can be by a factor of 2-4, depending on the lithotype. Figure 2.1
presents the dependency of some major lithotypes, where the values are
computed with Eq. (2.10) without considering changes in conductivity due to
temperature. If both porosity and temperature dependency are taken into
account, the increase in conductivity values due to pore volume reduction is
compensated after a depth of approximately 3000 m by the decrease in thermal
conductivities due to higher temperatures for most major lithotypes such as
shale, limestone, and sandstone. However, in case of salt and quartzite the
dependency on temperature is dominant so that the effect of pore volume
reduction is overwhelmed, as shown in Fig. 2.2.
Burial of sediments is of course generally associated with compaction
(porosity reduction) and with temperature increase which, in addition to dif-
ferent lithotypes, causes variations of thermal conductivity with depth and time.
These changes must be taken into account when heat conduction is calculated.
0.8
----KSH
- - -KSST
- - - - KLMS
0.6 --KSLT
<l> 0.4··
0.2
Fig. 2.1. Changes in thermal conductivity of the sediments (grains+pores) shale (Ksh),
sandstone (Ksst), limestone (Klms), and siltstone (Kslt) due to the varying porosities. Thermal
conductivities of the pure lithotypes and water (Kw) used for the calculation are:
Ksh = 1.98 W/moC; Ksst = 3.16 Wlm DC; Klms = 2.83 Wlm DC; Kslt = 2.22 Wlm DC;
Kw = 0.60 Wlm DC
Thermal History of Sedimentary Basins 81
5000
:[
6000 m
%
I-
Q.
W
c
!P 8000 m
S
'"
~ Thermal Gradient
<4
If! • 20 · C l km
1000 ,;} ~ 30 · C Ikm
Fig. 2.2. Vertical thermal conductivity of porous rocks during burial, with two different
thermal gradients. (Ungerer et al. 1990)
The capability of a body to store heat is expressed in terms of its specific heat.
H gives the energy used or liberated in a change in temperature in terms of
mass. Accordingly, it has an obvious effect on heat conduction under transient
temperature conditions. It does not playa role under steady-state conditions
where temperatures remain fixed.
As in the case of thermal conductivity for the specific heat prediction of
porous sedimentary rocks, one must know the ratio and specific heat of the
matrix and pore filling material. A weighted averaging can then be applied to
find the specific heat of the sediment. Porous sediments have a high specific
heat since water, the most common pore filling material, has an extremely high
specific heat value (c = 4.2 Ws/g Kat T = 20°C) compared to the mean value
of rocks (c = 0.8 Ws/g K at T = 20°C). Specific heat of sedimentary rocks
82 M.N. Yalpn et al.
2.4.2
Heat Transfer in Sedimentary Basins by Convection
Natural Convection
Forced Convection
quently the amount of heat stored in water is generally very limited. Thermal
energy transferred by compaction-driven water flow is therefore negligible,
unless it is concentrated in a very narrow zone. Release of confined water in
sediments of overpressured zones may occur at a geologically fast expulsion
rate. However, under realistic geological boundary conditions, duration and
areal extent are insufficient to cause thermal anomalies affecting the heat
distribution in sedimentary basins (Hermanrud 1986; Wygrala 1989).
Temperatures in sedimentary basins may also be affected by the convective
heat transfer induced by groundwater flow through regional aquifers. This kind
of water flow takes place in so-called hydrodynamic or artesian systems.
Pressure gradients caused by pieziometric/topographic conditions lead to flow
of water from recharge areas, which are topographically high, to discharge
areas located in down-dip areas. Hydrodynamic water flow, which is controlled
by the amount of water supply, the permeabilities within the aquifer, and
topographic variations, plays a major role in heat transfer in sedimentary
basins as discussed in detail by Smith and Chapman (1983) and Woodbury and
Smith (1985). Effects of regional groundwater flow in artesian systems and its
role in heat flow distribution have been investigated in many areas of the
world. Examples are the Williston Basin in the United States (Gosnold and
Fisher 1986), the Alberta Basin in Canada (Majorowicz et al. 1984), the Ero-
manga Basin, a part of the Great Artesian Basin in Australia (Chapman 1981),
and the North Sea (Andrews-Speed et al. 1984). Each of these studies de-
monstrates that temperatures in the basins are affected considerably by
groundwater flow. Temperatures are low in recharge areas due to the cold
meteoric water entering and penetrating the aquifer. Water which is heated in
deeper parts of the basin during transport results in anomalously higher
temperatures at discharge areas. Whereas the cited examples are of regional
nature, the same mechanism may also cause local disturbance of the tem-
perature field in areas where an upward movement of thermal water is ob-
served. Almost all thermal springs are related to fault and fracture zones
enabling the upward movement of waters and causing local disturbances of the
regional thermal field. Although the effects are local, thermal water springs are
a good indication of deep-seated thermal anomalies. Some fault or fracture
zones also act as sites of recharge. Hence an opposite effect, namely cooling of
the system, would be the result. The general conclusion is that natural (free)
convection and water flow forced by compaction and release of overpressuring
do not playa crucial role in heat transfer. Only forced convection related to
pressure gradients in hydrodynamic groundwater flow systems has a sig-
nificant effect and must be taken into account for the reconstruction of tem-
perature histories in sedimentary basins.
2.4.3
Boundary Conditions of Heat Transfer in Sedimentary Basins
In order to compute heat transfer in basin fill, physical and thermal conditions
at the base and the top of the sedimentary basin must be considered. The lower
boundary condition is determined by the heat flux density, which controls heat
84 M.N. Yalpn et al.
The heat flux density is a measure of heat flow per unit time and unit area. It is
often referred to as "heat flow". Sources of heat from the earth's interior are in
general the upper mantle and the lower crust. Heat flow from the lower crust
stems from the decay of radioactive isotopes, such as uranium, thorium, and
potassium and is called the radiogenic heat flow. The remaining portion, called
subcrustal heat flow, is related to the cooling of the earth. The relative pro-
portions of these two components depend on many factors. However, the main
control is thickness of the crust, as shown by Bodri and Bodri (1985; Fig. 2.3).
However, Royden (1986) cautioned as to this oversimplified relationship be-
tween crustal thinning and heat flow increase and gave examples in which the
increase is much higher than expected. Another correlation of heat flow is with
tectonic age, where heat flow of tectonically young areas are much higher than
the old cratons (Vitorello and Pollack 1980).
120 , - - - - - - - - - - - - - - - - - - - ,
100
'"E
~
.s 80
:s:
9u...
~ 60
w
I
40
20 L-_~_~_~ _ _L_~_~_~_~
10 20 30 40 50
CRUSTAL THICKNESS (km)
Fig. 2.3. General correlation of heat flow and crustal thickness for tectonic structures such as
young Cenozoic tectonic formations, tectonic structures, with thin crust at the subsided
peripheral parts of platforms and ancient platform structures of Precambrian age. (Bodri and
Bodri 1985)
Thermal History of Sedimentary Basins 85
Heat transfer mechanisms between upper mantle, lower crust, and into the
basin (upper crust) are yet unclear and sometimes controversial. Transfer by
radiation can be excluded. However, whether heat transfer by conduction is
really the dominant mechanism, or whether convection can playa decisive role
under certain circumstances (Welte 1995) has yet to be investigated in detail.
Theoretical concepts of thermal processes and events in the upper mantle and
lower crust must be linked convincingly with an increasing data base on the
temperature history of sedimentary basins. Heat input into a sedimentary
basin from its base must be entirely controlled by radiogenic and sub crustal
heat flow. However, in areas where a basin is formed on a sedimentary base-
ment, which is frequently the case, effects of this basement can drastically
modify the lithospheric heat flow. As has been established, in the sedimentary
basin fill a major heat transfer mechanism is thermal conduction, and differ-
ences in thermal conductivity in space and time within the basin fill are
therefore the most important factors controlling thermal irregularities (Welte
1995). Differences in thermal conductivities can be caused by primary effects of
lithologic properties (shale, sand, salt, etc.) or induced by geologic processes,
such as subsidence and sedimentation, generation and migration of hydro-
carbons (especially gas) or overpressuring. Considering the entire heat budget
of a sedimentary basin, fluid flow is only of minor importance and responsible
for rather local temperature anomalies. For regional temperature anomalies
within a basin, deep-reaching groundwater flow or water flow caused by hy-
drodynamics of overpressured strata are the main factors (Majorowicz et al.
1984, 1986; Andrews-Speed et al. 1984; Luheshi and Jackson 1986).
Measured regional heat flow values reveal important variations. Low values
of 30-40 mW/m2 are typical for old cratons such as the Baltic and Canadian
shields and for oceanic trenchs. High heat flow values of 85-120 mW/m2 are
measured in oceanic ridge or active volcanic areas. Regions of extensional
tectonics such as the Red Sea area and the basin and range areas of the western
United States also have high heat flow values. The overall average value for heat
flow is given by Lee (1963) as 63 mW/m2 • According to Kappelmeyer and
Haenel (1974), the average for oceans is 61 mW/m2 and for all continents
60 mW/m2. Regional variations in surface heat flow, as compiled by Allen and
Allen (1990), is given in Table 2.1. Their "worldwide" average value is higher,
69.6 mW/m2, than those cited above. Although it is risky to generalize, an
assignment of heat flow values (value ranges) to basin types is possible. A basin
classification based on regional plate tectonic concepts, as proposed, for ex-
ample, by Kingston et al. (1983a,b), is suitable for such an assignment. Some
general results, as outlined in Fig. 2.4, have emerged: (1) ocean ridges, intra-arc
basins, active rift areas have higher than normal heat flow; (2) stable cratonic
areas, fore-arc basins have lower than average heat flow values; (3) young
orogenic areas (suture zones) have high heat flow values.
If the actual aim is the reconstruction of temperature history of sedimentary
basins, then not only the present values of heat flow but also the ancient values
(paleoheat flow) must be known. Several attempts have been made to estimate
paleoheat flow. The approach of McKenzie (1978, 1981) is a typical example,
where the temporal changes in heat flow is calculated for a basin formed by
86 M.N. Yal~m et al.
mW/m2 HFU
extension. The period of stretching and thinning of the lithosphere and up-
rising of the asthenosphere is associated with an increase in heat flow, which is
quantitatively determined as a function of stretching factor (~) and time
(Fig. 2.5). The so-called thermal subsidence period following the termination
of stretching is represented by a decrease in heat flow over time due to the
relaxation of lithospheric isotherms to their original position before stretching.
Several modifications to the McKenzie model and also new geodynamic models
have been proposed for the definition of basal heat flow as a function of time
(Sclater and Christie 1980; Wernicke 1985; Royden 1986; Burrus and Bessis
1986). Although these models contributed much to the understanding of
crustal and mantle thermal phenomena, they are still not sufficient to provide
reliable data on heat flow variations with time, as our present knowledge of
geodynamic processes is not precise enough (Tis sot et al. 1987, Welte 1995).
Consequently the history of the basal heat flow must be considered a "best
estimate" parameter, which can be adjusted with the help of other, in-
I I f ,
, \ Intracon-, ' Rift, '
t{\lc\IO(\ \ \ tinental, ~asin' : Passive' Ivt:
~oes
\ C{\ls\a: .(\s
"' b 'ns'
,asl , '
., , ,marg"
,b . In, b/doce
. afJic '
".,
\ ba.sl " , . . aSlns ' aS1fJs I rafJSf.
\\ ~
. + 'I,.Orr n'
aull I I
\ +
~++~+ bas ' I
. + ~ - ~,'
. - -....
-.
~+:::, "I ir ~ rr
~
--f...
Fig. 2.4. Relative changes in heat flow in different types of sedimentary basins in respect to
plate tectonics. (Y al~m and Welte 1988)
Thermal History of Sedimentary Basins 87
........
en
o.i
E 2
--tU
()
3x
::J
u::
til
(I)
I
o ~--~------~------~------~------~------~--~
o 20 40 60 80 100
t (Ma)
Fig. 2.5. Changes in heat flux as a function of time for various values of ~. (McKenzie 1978)
Surface Temperatures
ignored since their effects are not distinguishable. Definition of the surface
and/or sea bottom temperatures requires consideration oflong-term variations
in surface temperatures during geological time. Although an accurate de-
termination of those variations is still not possible, facies studies of sedi-
mentary units, fossil fauna and flora, ratio of oxygen isotopes, and plate
tectonic reconstruction of continents and oceans allow the derivation of
temperature variations during the geological past (Meyerhoff 1970; Schwarz-
bach 1974; Frakes 1979; Frakes et al. 1994; Habicht 1979; Smith et al. 1981;
Parrish et al. 1982; Ziegler et al. 1984).
Approximation of the surface and/or sediment/water interface temperatures
for a given sedimentary basin requires the following:
- The paleolatitude position of the basin through geological time using pa-
leogeographic maps such as those by Smith et al. (1981) or by the Paleo-
geographic Atlas Project (Ziegler 1987).
- The mean annual paleoair temperatures as derived from maps of global
paleotemperature distribution for a given geological time slice. Wygrala
(1989) prepared a chart of mean surface paleotemperatures vs. latitude vs.
geological time from the Carboniferous to the recent past (Fig. 2.6) from
which a time-temperature curve can easly be derived.
- Contemporary surface temperatures. Corrected mean air temperatures can
be used directly as the surface temperatures for periods of erosion or
continental deposition. Due to the complex interactions between air and the
surface caused by vegetation and soil/rock type, but also by local climatic
conditions, no clear rules exist for this matter; addition or subtraction of 1-
2 DC from the mean air temperatures is recomended by Haenel (1971) and
Clauser (1984), respectively.
- Contemporary sediment/water interface temperatures. Here, effects of water
depth, paleogeographic position of the basin and global oceanic currents
must be taken into account; except for some shallow marine depositional
enviroments (approximately water depths up to 60-200 m), the relevant sea
bottom temperatures are determined by the coldest water temperature en-
countered within the specific marine system. In open marine systems, for
example, the relevant value is that of the polar waters, at present 2-4 DC, but
remarkably higher during preglaciation periods (Frakes 1979). The present
Mediterranean Sea is a typical example of a closed marine system where sea
bottom temperatures are not affected by global oceanic currents, and where
sea bottom temperatures are therefore not less than 13 DC even at depths
exceeding 2000 m (Wygrala 1989).
Despite all of these considerations it cannot be asserted that the determi-
nation of surface and sea floor temperatures is entirely correct. However,
sensitivity of temperature history to the upper boundary condition can be
tested, and a calibration can be carried out (see Sect. 2.5).
>-l
TIME ( Mabp) - ::r
(I)
Fig. 2.6. Surface temperatures vs.latitude vs. geological time (Wygrala 1989), Global mean temperatures are based on Frakes (1979). Geological age
ex>
scale is taken from Harland et al. (1989) '0
90 M.N. Yalpn et al.
2.4.4
Other Factors Affecting Thermal History of Sedimentary Basins
X 3
Ii:w
C 4
" .6
,,
5
,,
6~----------------------~--------------~~------~'~--~
+q
Fig. 2.7. Effect of heat generation in sediment (A) and thermal conductivity (K) on the
temperature-depth profile. Temperature curves are calculated with the given K and A values
and from Eq. (2.13) for H = 6 km and with q = 70 mW/m2 and To = 10 °C (Rybach 1986).
(Reprinted from Rybach L Amount and significance of radioactive heat source in sediments,
pp 311-322, 1986, with kind permission from Editions Technip, Paris)
Table 2.2. Average contents of heat producing radioelements in sedimentary rocks. (Rybach
1986)
Carbonates 2.6
Limestone 2.0 1.5 0.3 0.75 0.62
Dolomite 1.0 0.8 0.7 0.80 0.36
Evaporites
Salt 0.02 0.01 0.1 0.50 2.2 0.012
Anhydrite 0.1 0.3 0.4 3.0 2.9 0.090
Shales, siltstones 3.7 12.0 2.7 3.2 2.4 1.8
Black shales 20.2 10.9 2.6 0.54 2.4 5.5
Sandstones 2.4
Quartzite 0.6 1.8 0.9 3.0 0.32
Arkose 1.5 5.0 2.3 3.3 0.84
Graywacke 2.0 7.0 1.3 3.5 0.99
Deep sea sediments 2.1 11.0 2.5 5.2 1.3 0.74
aBroad average since density strongly depends on porosity. (Reprinted from Rybach L
Amount and significance of radioactive heat source in sediments, pp 311-322, 1986, with kind
permission from Editions Technip, Paris)
92 M.N. YalyIn et al.
~========================~~Om
-.40------------------------------------------- 1000 m
----------------_._----------_._---
2000m
_-- 80 ---._____ -_".---.-.-..........______ ------... -
6000m
7000m
by conduction, the temperature increase with time (i.e., depth) is also con-
trolled by thermal conductivity.
A general statement on the affects of radioactive heat generation in sedi-
mentary basins is difficult. However, if a basin is deep enough (>5 km), if the
major lithologies are fine clastics, and if the basin fill is not very young
(> 10 Ma), one must consider the internal radioactive heat generation in
modeling the temperature distribution.
Thermal Refraction
2.5
Reconstruction of Thermal History in Sedimentary Basins
- For radiometric systems, such as K-Ar, Rb-Sr, and U-methods, which are
closed at different temperatures, a combination of radiometric age de-
terminations can be used for thermal history reconstructions as indicated by
Buntebarth and Stegena (1986).
Considering the limitations of the various approaches noted above it seems
that methods based on physical concepts and numerical simulation are the
most suitable for reconstructing the thermal history of sedimentary basins. In
other words, the temperatures within a basin must be calculated by solving the
heat transfer equation given in Eq. (2.9). As stated above, thermal history is
linked to the basin evolution, which is a dynamic, complex, and a multi-
parameter system with boundary conditions changing through time. Ad-
ditionally, processes and parameters which control the temperature
distribution are closely interrelated and influence each other. The consequence
is that calculation of temperatures during basin evolution requires an in-
tegrated and quantitative approach and a suitable modeling method. Either of
two main modeling techniques, namely forward and inverse modeling, can be
applied to predict temperature history. Inverse modeling is used mainly to
determine paleoheat flux, either with the help of measured vitrinite reflectance
values (Lerche et al. 1984) or of fission track analysis results (Huntsberger and
Lerche 1987). Forward modeling is applied to problems of hydrocarbon gen-
eration prediction (Tissot and Espitalie 1975) and to model geological pro-
cesses during basin evolution (Yiikler et al. 1978; Welte and Yiikler 1981; Welte
and Yalym 1985; Yalpn 1991). The latter (computer-aided basin modeling)
seems the most suitable method to handle dynamic, complex and integrated
systems in a deterministic manner.
2.5.1
Reconstruction of Thermal History by Computer-Aided Basin Modeling
ensured. Equations used in the system are formulated in such a way that almost
all are coupled with each other via common parameters. Hence the simulation
represents a fully integrated basin modeling approach. The following processes
can be simulated: (a) deposition, (b) nondeposition, (c) erosion, (d) faulting,
(e) thrusting/overthrusting, (f) halokinetics, (g) compaction, (h) pressure
build-up, (i) heat transfer, (j) maturation of organic matter, (k) oil and gas
generation, and (1) expulsion of oil.
Most of these processes affect the thermal history and vice versa. Processes
such as maturation of organic matter and petroleum generation are, on the
other hand, controlled by the temperature history. During the simulation of
basin evolution heat flux density at the base of the system and surface (and/or
sea floor temperatures) are used as the thermal boundary conditions. Thermal
conductivity, specific heat, density, compressibility, permeability, initial po-
rosity of sediments of different lithotypes, and viscosity and density of pore
fluids are important parameters employed during the calculation procedures of
the modeling routine.
One starts with modeling at a given time in the geological past and simulates
the temporal development until the present. As a consequence the input data
must be prepared in an appropriate way so that the entire temporal develop-
ment is represented by the data. This requires a systematic consideration of the
geological history using all available data. However, knowledge on basin his-
tory is often limited, and some of the paleoparameters can be estimated only
using indirect approaches. Estimation of paleo heat flow and paleoclimatic
conditions or erosional amounts are typical examples. Therefore prior to the
mathematical model a so-called conceptual model must be designed. The
conceptual model forms the basis for the model input (Welte and Yalpn 1985)
and must be calibrated by comparing the first simulation results with observed
data. In most cases an iterative approach is needed to reach an acceptable fit
between simulated and observed results. The main point during the con-
struction of the conceptual model is definition of the geochronological units.
Structuring of the input data is based on this temporal subdivision in term of
events. Time periods which are not represented by physically existing units,
such as erosional periods, must also be identified and included. The event-
based structured input data consist of absolute geological age and duration,
present and eroded original thickness of deposited units, lithology, present
porosity, water depths, heat flow at the base of the system, and surface or
sediment/water interface temperatures at the top. Additional input data are the
physical properties of different lithotypes and formation water, and for pur-
poses of hydrocarbon generation and expulsion the type and amount of or-
ganic matter.
The typical outputs of the model for each event consists of thickness,
porosity, pore pressure, temperature, maturity, level of hydrocarbon genera-
tion, amount of generated hydrocarbons, and the expulsion efficiency as a
function of time. Almost all of these parameters can be used directly or in-
directly for calibration purposes by comparing the values calculated by the
simulation for the present time with measured data. After the calibration of the
conceptual model a sensitivity analysis can be performed by changing selected
96 M.N. Yal~m et aI.
2.5.2
Controls of Thermal History
The PDI basin modeling system has been used to demonstrate the effects of
various processes and parameters on thermal history. For this purpose some
hypothetical cases of one-dimensional simulations are first carried out. To
visualize the effects of different parameters on thermal history a case history is
simulated as a reference well. Other wells are then simulated in which only one
parameter is changed. Comparing the computed temperature values in each
case, reference well and the well with the changed parameter, the effect of the
relevant parameter is discussed.
The reference case represents an uninterrupted deposition of a 2400-m-
thick sandy shale sequence over 120 million years (Ma) with a sedimentation
rate of 20 m/Ma. Forty events are distinguished, each of 3 Ma duration.
Boundary conditions remained constant over the entire time. Heat flow at the
base was chosen to be l.2 HFU and sediment/water interface temperatures
14°C. The water depth was set at 100 m. Simulation was carried out in time
steps of 1 Ma. The complete form of the input data is given in Table 2.3.
Results are demonstrated using various diagrams (Figs. 2.9-2.11) displaying
temperature vs. depth at present, temperature vs. time of the lowermost unit,
and a corrected burial history diagram with temperatures. Figures 2.9-2.11
refer to the reference well. Computed values show that temperature at the
base of the sequence increases to 82.5 °C at a depth of approximately 2500 m,
where the actual thickness of sediments is 2400 m (Fig. 2.9). The difference of
100 m is the water depth at present. Due to the uniform boundary conditions
an almost constant geothermal gradient of 28 °C/I000 m is established. For
the same reason temperatures increase very gradually with a constant rate of
0.6 °C/Ma (Fig. 2.10), and as shown by the burial history diagram where
isotherms remain horizontal during the entire period of deposition
(Fig. 2.11).
The rate of deposition may effect the temperature distribution even if all other
parameters remain constant. Extremely fast sedimentation rates can lead to
decreased temperatures if the sedimentation is faster than the rate of thermal
Thermal History of Sedimentary Basins 97
Time: present
Temperature (OC)
Event Lit. 0 30 60 90
0
40 layer 40 5
39 layer 39 5
38 layer 38 5
37 layer 37 5
36 layer 36 5
35 layer 35 5
500 34 layer 34 5
33 layer 33 5
32 layer 32 5
31 layer 31 5
30 layer 30 5
29 layer 29 5
28 layer 28 5
27 layer 27 5
26 layer 26 5
1000
--
25 layer 25 5
24 layer 24 5
23 layer 23 5
22 22 5
E 21
layer
layer 21 5
20 layer 20 5
....
.c:
C. 1500
19
18
17
layer
layer
layer
19
18
17
5
5
5
Q) 16 layer 16 5
15 layer 15 5
C 14 layer 14 5
13 layer 13 5
12 layer 12 5
11 layer 11 5
10 layer 10 5
2000 9 layer 9 5
8 layer 8 5
7 layer 7 5
6 layer 6 5
5 layer 5 5
4 layer 4 5
3 layer 3 5
2 layer 2 5
I layer 1 5
2500
3000~--------~~~------------------~
Fig. 2.9. Simulated temperature vs. depth trend of the reference well
high water content. The thermal effect of overpressuring was observed when
the sedimentation rate was increased to 300 m/Ma. In this case temperature at
the base of the sequence increased to 93 °C due to a decrease in thermal
conductivity resulting from high porosities of the overpressured system
(Fig. 2.12, line A).
Thermal History of Sedimentary Basins 99
Layer: layer 01
Temperature rC)
Event Lit.O 15 30 45 60 75 90
0 40 layer 40 5
39 _layer 39 5
38 laye( 38 5
37 layer 37 _ 5
36 layer 3.6 5..-
35 layer _35 _ 5. .
34 layer 34 5
:13 layer 33 5
~ layeL 32 _ .5
31 layer 31 5
30 layer 30 _ 5
29 layer 29 5
28 laye! 28 5
40 27 layer 27 5
-.c
26 layer 26 5
25 layer 25 5
24 layer 24 5
Q. 23 layer . 23 5.
-
22 _layer 22 5_
ea 21 Ja)/er 21
20 layer 20
_5_
5
:E 19 layer 19 5
_ 18 layer 18 5
CI,) 17 layer 17 5
E 16 layer 16
15 layer 15
5
5
t= 80 14 layer 14
13 layer 13
5
5
12 layer 12 5
11 layer 11 5
10 layer 10 5
9 layer 9 5
8 ayer
l 8 5
_ 7 layer 7 5
6 layer 6 5
5 la)ler 5 5
4 layer 4 .5
3 layer 3 5
2 layer 2 5
120 1 la er 1 5
500
1000
E
.c
a.. 1500
QJ
Cl Temperature (0C)
_ 10 - 20
2000 20 -30
30 - 40
40 - 50
50 - 60
2500 D 60 - 70
1::: ti 70 - 80
o above 80
o A- . - 300 m/Ma
B- shale
\ e salt
\ ~ D- . <'1>=% 20
\ ~, E .. <'1>=%10
F-
\ 'R,\"
\
R
HF= 1.6 HFU
reference well
,1\\
, '\ "
500 - \ \ ,~ , \ , \
\
\' \\ '
\ :~ \' \
\,0"
" \\ \
\~, \ "
\'
,~, \ \ '
\ \'.
\
\, \' \
\ ''\ \ '
1000 \ \ ' \ ,
, \\ \
\ '\ \ '
g \
\ \'.
,\ \ \
\
..c: \ \', \' \
li
(!) \ '\ \ \ ,
0 \' \ '\ \
\ \ \ \'
\ ", \\ \
1500 \ \ \ \ \ '
\ \ ''\ \' \ \
\
\
'\ \\ \\, \
,',
"
\
'
\ \ \ '\
, \,
\ \ \ \ \
\' \\
'\ \, \
\
2000 \
\' \ \
\ \ \ '\ \
\ \ ,
\ \, '\ \ \
\ \
'.
'
\', \
\ \
\ \ \ \
\ \ ' \
\ \
\
\ A\
2500
o 20 40 60 100
Temperature (DC)
Fig. 2.12. Various temperature vs. depth trends which are calculated with only one varying
parameter with otherwise constant parameters. Effects of different lithologies, porosities, heat
flux densities, and sedimentation rates are demonstrated
102 M.N. Yalpn et al.
Table 2.4. Thermal properties of the lithotypes sandy shale, shale, and salt which have been
used for the simulation of case histories
To show the effect of porosity the reference well is simulated in such a way that
porosities remained constant, both as a function of time and depth during
deposition. Two cases are simulated, one with 10% porosity and another with
20%. A higher porosity, for example, higher water content, diminishes the
thermal conductivity of the sedimentary sequence. This results in a decrease in
conducted heat and hence a lower heat loss at the surface. Consequently, the
temperature could rise to 79°C in the well exhibiting higher porosities,
whereas it remained at 74 °C in the well with a porosity of 10% (Fig. 2.12 lines
D and E, respectively).
The type of the formation fluid also influences the temperature history.
Changes caused by salinity differences are negligible. However, when forma-
tion water is replaced by oil and/or gas, the effect on the bulk thermal con-
ductivity may be remarkable, as thermal conductivities of oil and gas differ
considerably from those of water. Because thermal conductivities of oil and gas
are lower, the bulk conductivity of a hydrocarbon saturated sediment drops.
Normally only reservoirs, and to a certain degree carrier beds, are saturated
with oil or gas. In such a case the thermal properties of the respective sequence
must be specifically defined. Zwach (1995) showed such an effect in the Alberta
Deep Basin.
The effect of heat flow on thermal history is obvious since it defines the energy
input into the system. Therefore temperature and heat flow are directly pro-
portional, as also indicated in Fig. 2.13, where the present temperature dis-
tribution of the reference well is compared with another well. In this well heat
flow is increased from 1.2 to 1.6 HFU and temperature at the base increased
accordingly from 81°C in the reference well to 104 °C in the other well
(Fig. 2.13, line F). The relationship between heat flow and temperatures is also
demonstrated where a simulation with varying heat flow histories is carried
out. For this simulation everything except the heat flow is taken as it was in the
reference well. In the other well heat flow was constant as 1.2 HFU during the
first 21 Ma of the basin evolution. For the next 21 Ma it increased to 1.3 HFU
and then gradually up to 1.8 HFU during the next 21 Ma. For a period of 9 Ma
it remained at this level and then decreased gradually to 1.3 HFU. Input data
Layer: layer 01
Sedimentation Rate SWI Temperature >-3
(m/Ma) (0C) Heat Flow (H FU) Temperature (0C) ::r
Fig. 2.13. Effects of a variable heat flux density on the temperature history. Other simulation parameters are kept as those of the
reference well
104 M.N. Yal~In et al.
used for this simulation and resulting temperature history of the lowermost
(layer 1) are shown in Fig. 2.13. The direct relationship between changes in
heat flow and temperature of the sediment is clearly demonstrated.
depositional periods are added (Fig. 2.15). The first two periods have the same
duration of 18 Ma. However, the first nondeposional period began after a
deposition with a sedimentation rate of 40 m/Ma, whereas the second ensued
after a rate of 20 m/Ma. The last nondepositional period lasted only 3 Ma. In
all three cases the temperatures decreased within the first 3 Ma following the
initiation of the nondeposition periods. They then remained constant until the
next depositional period began. It is interesting to note that cooling was faster
during the nondepositional period after the rapid deposition (phase I), and
much slower following the period with lower sedimentation rates (phase 11).
During phase III cooling started even before the onset of nondeposition due to
a decrease in the sedimentation rate from 40 to 20 m/Ma during the event just
prior to nondeposition {Fig. 2.15}. Both the sedimentation rate and the type of
lithology plays a role. The sandy shale used for the simulation has moderate
thermal conductivity but a relatively high heat capacity. These resulted in a
long reequilibration time of the temperature distribution.
Erosion is also associated with cooling and occurs during the entire ero-
sional period, as shown in Fig. 2.16. There is a direct correlation between the
amounts of cooling and erosion. Temperature dropped from 78 to 42°C
during the erosion phase I, where during 9 Ma, 810 m were eroded. During the
erosion phase II, also lasting 9 Ma, 360 m is eroded, with a corresponding
temperature decrease of only 13 °C. Erosion leads not only to a decrease in
temperatures but also to changes in the geothermal gradient. Figure 2.17
presents the burial history diagram of the hypothetical well and the corre-
sponding change in the isotherms during geological history. Prior to the ero-
sion phase I the average geothermal gradient was 34 °C/I000 m. At the end of
the erosional period the value dropped to 26 °C/I000 m. A similar trend can be
observed during the erosion phase II as indicated by the deepening of iso-
therms {Fig. 2.17}.
Whereas erosion leads only to vertical changes in basin stratigraphy, most
structural deformation is associated with lateral displacement. Particularly
faulting, thrusting, and diapirs cause drastic changes in the continuity of
layers, both in vertical and lateral direction. The displacement of sediments
affects both the conductive heat transfer and the water flow in the system. A
certain amount of heat can be transferred by such displacements if the
movement is rapid enough. However, such movements are generally too slow,
and the amount of heat which is transported by mass convection is negligible
except in cases of rapid overthrusting (Wygrala et al. 1990; Yalpn 1991).
If along a cross section only a single point is considered, normal and growth
faulting often results in a thickness reduction of the relevant unit. The thick-
ness reduction is normally compensated by the increased sedimentation rate
on the downthrown block of synsedimentary (growth) faults and by enhanced
erosion on the upthrown block of a normal fault. In both cases the config-
uration of the layers prior to faulting changes drastically, and the conductive
heat transfer in vertical and lateral directions is affected. Figure 2.18 presents a
cross section from the Central Graben area of the North Sea illustrating the
formation of a synsedimentary fault. The fault was active during the deposition
of units 5 to 17 as indicated by thickness variations. Figure 2.19A shows the
Temperature ( °C ) Temperature ( °C )
....,
::r'
L ...... ... I ;t U to 20 30 40 50 60 7,0 80 0 ,,0
1.0 ~O ~O 9,0 I a 1'O"ent
...'"
,~ ~/~' .-
S
5 ~Q -'!,~er. 40 e:...
39 layer 3~ 5 5 39 layer 39
38 layer 38 5 III 5 38 layer ~
::c:
tn'
3] layer 37 5 5 :)7 layer 37
5
0...
3~ Ia~er ~ 5 36 layer 36 -<
3_5 Ia~er 35 _ 5" 5 35 layer 35 0
34 layer 34 5 5 34 layer 34 -.
3.3 !ayer 33 5 en
5 33 layer 33
32 layer 32 5 5 32~ayer .!J2 '"0..
.ill layer 31 5 5 31 layer 31 S'
30 layer 30 5 5 30 layer 30 '"g
29 layer 29 5 5 29 lay!r . 2~
28 layer 28 5 5 ~8 laye, •. 28
'"...
-<
40 i7 !ayer ~7 5 5 27 layer 27 tJj
2§..layer 26 5 5 26 layer 26
25 layer 25 5 5
'"en~.
25 layer 25
Ci: 24 layer 24 5 5 24 layer 24
.D
ro 23 layer 23
22 layer 22
5
5
} 5 23 laye, 23
5 22 laye, 22
:2: 21 layer21 5 5 2 1 layer 21
-Q) 20 layer 20 5 5 20 layer 20
19 layer 19 5 5 19 laye, 19
E 18 layer 18 5 5 18 layer 18
~ 17 laym 17 5 5 17 layer 17
16 layer 16 5 5 16 layer 16
15 layer 15 5 5 15 laye, 15
80 14 layer 14 5 5 14 layer 1 4
13 laye, i:3 5 5 13 ayer
l 13
12. layer 12 5 5 12 layer 12
11 layer 11 5 5 11 layer 11
10 layor 10 5 5 10 layer 10
9 layer 09 5 5 9 layer 09
8 layer 08 5 5 8 layer 08
7 layer 07 5 Ii 7 layer 07
6 layer 06 5 5 6 layer 06
5 layer 05 5 5 5 layer 05
4 layer 04 5 5 4 layer 04
3 layer 03 5 ( B) 5 . ~ layer 03
2 layer 02 5 5 2 layer 02
120 I "D'~' U, I U I I 5 1 laver 01
r I
o
Fig, 2.15. A Temperature history of the lowermost unit in a well similar to the reference well where, however, three nondepositional "
periods (r, II, III) are integrated. B For comparison, the temporal development in the reference well
Layer: layer 01 o
00
Sedimentation Rate SWI Temperature
-
(m/Ma) (0C) Heat Flow (HFU) Temperature (0C)
30 60 90 o 4 8 12 16 0.0 0.4 0.8 1.2 o10 2030 40 50 60 70 80 90
o '-40 layer 40
39 layer 39
38 layer 38 }ll
37 layer 37
36 layer 36
35 layer 35
34 layer 34
33 layer 33
32 layer 32
31 layer 31
30 layer 30
29 layer 29
28 layer 28
401 27 layer 27
26 layer 26
25 layer 25
24 layer 24
0: 23 layer 23
..0 22 layer 22
ctl
21 layer 21
~ 20 layer 20
-Q) 19 layer 19
16 layer 16
E 17 layer 17
F 16 layer 16
15 layer 15
801 14 layer 14
13 layer 13
12 layer 12
11 layer 11
10 layer 10 s::
9 a
l yer 09
6 a
l yer 06
~
7 a
l yer 07 -<
6 al yer 06
eo.
-<)
5 layer 05 s
4 layer 04 ~
3 layer 03
2 layer 02 ~
laver 01
120 '
Fig. 2.16. Cooling caused by erosional periods (I, II) demonstrated in a well. Some of the input data are also shown
o~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~~
...,
::T'
!ll
aeo.
500 ::c
c;;.
(])
<.,) o
..,
'<:
ro
......
~
o.....
::J en
CI)
...... 1000
'"0-
c s'
(]) '":lor
E ~
"0 o:l
."
(])
CI) '"
s·
1500 '"
~
o
Q)
..c
.........
E
......... 2000
Temperature (OC)
..c
0.. 10 · 20
Q) 20 · 30 6T =36·
o 30·40
2500 40 · 50
50·60
60 · 70
70·80 6T = 13°
B ABOVE 80
3000~1-----------------------,-----------------------,-----------------------+~
120 80 40 o
Time (Mabp) o
'CJ
-
Fig. 2.17. Burial history diagram of the well with two erosional periods (I, II) where isotherms are also shown. Note that the geothermal
gradient becomes lower during the erosional periods
A B
A
m248M~ ~,~
B
2
1000 1000
at 150 Mabp
A B
1000 1000
--
E
A B
...
17
.s:::::.
a.
Q)
1000 1000
0
2000 2000
at 65 Mabp
3000 A B 3000
3
23 1
16
1000 17 1000
2000 2000
3000 3000
at 38 Mabp
4000 4000
Thermal History of Sedimentary Basins 111
Fig. 2.18. Cross sections showing the formation of a synsedimentary fault in the Central
Graben Area, North Sea. Note that the lowermost layer is composed of salt, and that salt
movement also participated to the fault formation. Numbers indicate layers. (Modified from
Heynisch et al. 1987)
Temperature (OC) ......
......
tv
A B
[~~. ~:! O 50 100 150 o 50 100 150 200
# I0
20 29 1 2 20
28
40 40
25 I2 ... . .1 60
60
19 30
80 80
18 30
17 30
100 100
0: 15
.0 " 120
ell 120 20
~ "
13 18
12 8 140
W 140 11 ~
~ '" '"
9 2
~ 160 ... 160
6 180
180
5 1,6 200
200
220
18 s::
240
~
240 16 ><:
~
=1'
260 L-~~-------r-------r-------.------~-------.------~r-------r-------t1 200
-<1
:;
~
Fig. 2.19. Temperature history of layer no. 3 at points A and B on the cross sections shown in Fig. 2.18. A Affected by faulting. B Not ~
affected by faulting
_._._-- ',--...·----....... _.·40--' ... - ... - - - - - - ....... - ......
2000 2000
3000 3000
1000
2000
3000
,eo
4000 4000
1000 1000
,......
S
'-"
2000
..s0.. 3000
CI)
0 4000
5000
slow overthrusting
Gridpoints 5 10 15 20 26
10
100
200 ~~. 60 '~
--E 300
-
400
.c
a(I,). 500 ~~~~~~~~~~~~oo
0 600 6000
700 7000
800 8000
HORIZONTAL SCALE: 9000
2km ~ ~ ·60~ ~ . Isotherms (0C)
10000 10000
Fig. 2.21. Temperature distribution within the overthrust sheet and overthrusted units after a
slow (0.5 em/year) overthrusting. (Wygrala et al. 1990)
phase begins, during which the disturbed temperatures tend to reach balanced
normal values. Sensitivity runs indicate that within the first 1 Ma about half of
the difference between initial and final temperatures at the base of the entire
sequence has been reached. Complete equilibrium requires approximately 7-
rapid overthrusting
Gridpoints 5 10 15 20 26
20
-Ea .. '
~~~
~~
.-~----1I10---
~ .. ~'110·----12- 4000
.c ~~Tr_;~~r_~·1~2O~-~~~~~5000
(I,)
o 6000
7000
8000
9000
- - ·60- - -Isotherms (Oel
10000 10000
Fig. 2.22. Temperature distribution within the overthrust sheet and overthrusted units after a
rapid (5 em/year) overthrusting. (Wygrala et al. 1990)
Thermal History of Sedimentary Basins 115
2.5.3
Calibration of Thermal History
The conceptual model of basin evolution which forms the basis for the input
must be calibrated by comparing simulation results with measured/observed
data. Since almost all of the measurable parameters are either a direct result of
the temperature history or were at least influenced by it, there are usually
enough data from temperature-sensitive parameters to ensure a reasonable
calibration. Information useful for calibration is derived mostly from wells.
The relevant data are:
o 8. Temperature ( °C )
z ~
II i! 20 40 60 80 100 120 140 160 180 200 220 240 260 280 0 20 40 60 80 100 120 140 160 180 200 220 240 260 260 0 20 40 60 80 100 120 140 160 180 200 220 240 260 280
~ :5 0
o
20 38 \ (a) \. (b) \ (c)
500
19 38 \ \ \.
1000
18 38 \ 1\. ~
150 )
) 17 38 \ ~ '\\
200'
) 16 38 \\\\. ,\\
250 l'
300, ) 15 38 I' .\.\. '.\'\.
) 14 38 11\ '& \ \ .
350 '", \
) 13 38 .\ .... '\.
E 400
12 38 \ "t· .1 "\. \ \
450' )
.c: 11 38 ,\ .....". Diane of overthr stlna -.A , '\.
500 )
-
........
a. 550
) 10 38 I \ fl.1 \
'-"\. \ \.
<1> 38 II \ \ \ , \ ' \..
600 ) 9
o 38 11\ \ \ '~10_20my I' \
650 ) 8 '\ \ ....
38 I. \ \. \ I , \\. \ \ \
700 ) 7
) 6 38 0,1-~, I \ 0.1-T". \ \ '\' \ ' \
750'
,, \..._"\.
) 5 38 \~ \ \-10-20my 0.3~~,7my~\. 0.1-"\ \. ~10-20my
800
4 38 0.3 .... ' Y. \ 1 my'--""\ \ \ \ ~ 0.3-,"\ \ \ \"","1 my'\.
850 ) "\
38 1 my,"" \ \ \ - 7 my \', , '),. \ I '
, 7my ......
900 ) 3
38 \' \ \ \.\ , , ~ \. \ , , s::
950' o 2 \ "
1 38 \" , \. ~ " ~ \. " "'\. ~
1000 0 '. " "" >-<:
e.
-("\
Fig. 2.23a-c. Temperature vs. depth at overthrust step after overthrusting (during reequilibrium) sensitivity to lithology and different heat flow values. 5
a Dolomite over dolomite with a basal heat flow of 1.0 HFU. b Shale over shale with a basal heat flow of 1.0 HFU. c Dolomite over dolomite with a basal ~
heat flow of 1.6 HFU. (Wygrala et al. 1990) ~
Thermal History of Sedimentary Basins 117
The use of several calibration parameters would be the ideal and most
comprehensive manner of thermal history calibration. As emphasized by
Leischner et al. (1993), the combination of two independent sets of calibration
parameters, for example, one derived from maturation indices and another one
from geothermometry, is required for a reliable temperature history re-
construction.
The calibration process is based on modification of the conceptual model, as
permitted by relevant field and laboratory data, and on the adjustment of the
respective parameters on the input data. However, original input such as
thickness of the layers, type, age, and duration of various events, timing of
tectonic movements, depositional environment and related water depths, basin
type, and thermophysical properties of different lithologies are based on real
observations and measurements and therefore cannot be significantly modified
for calibration purposes. Consequently only sea bottom temperatures, heat
flux, timing and duration of erosional events, and original thickness of eroded
units are input data which can be adjusted within geologically acceptable
ranges to establish a fit between calculated and measured parameters. Of
course here are adjustment limitations even for these parameters. For example,
a heat flux density of 2.5 HFU could not be selected for forearc basins, which
usually have much lower heat flow values; or a sea bottom temperature of
18°C in a 1200 m deep open ocean would be unrealistic since sea water
temperatures drop very rapidly with increasing water depth (Fig. 2.24).
Thermal calibration has only a small degree of freedom, since physical,
chemical, and geological data and principles place severe constraints on the
procedure.
Although organic maturity indicators have a high sensitivity to thermal
history, an acceptable match for all the available calibration parameters should
be obtained for rigorous modeling. In certain cases a measured maturity trend
can be simulated with more than one version of a conceptual model. Con-
sideration of additional calibration parameters narrows the possible paths and
enhances the validity of the conceptual model. A typical example of the value of
independent calibration parameters was presented by Leischner et al. (1993). A
well in the Lower Saxony Basin in Germany, with a well-known burial history
(Fig. 2.25), was simulated to achieve an improved calibration of the tempera-
ture history. A suite of organic maturity parameters including Rock-Eval
pyrolysis, vitrinite reflectance, and methylphenantrene index calculations was
used. These were combined with inorganic temperature indicators such as fluid
inclusion measurements, fission-track studies, and illite crystallinity. The
combined data were used finally to calibrate the respective conceptual model of
basin evolution.
In this well vitrinite reflectance values increase from 0.55% Ro at approxi-
mately 500 m depth to 2.0% Ro at 3300 m (Fig. 2.26). This trend of vitrinite
reflectance is in good agreement with values of MPI and Tmax values. Thus the
reliability of the maturity trend is ensured. Fluid inclusions were found in
anhydrite veins within the Zechstein and Upper Carboniferous and in authi-
genic and detritial quartz from sediments of Late Carboniferous Age. Large
fluid inclusions in anhydrite veins located presently at depths of 1860, 2244,
........
00
200
400
600
I.c
800
a
Q)
"0
as 1000
1ii
~
2000
3000
is:
4000 fz:
>-<
e.
-<)
5
~
Fig. 2.24. Changes in water temperatures in open oceans as a function of depth. (Smith 1982) ~
Thermal History of Sedimentary Basins 119
WELLF
2000
I
a 4000
<ll
o
6000
"inversion event"
Fig. 2.25. Simplified burial history diagram of well F. C, Upper Carboniferous. (Leischner et al.
1993). (Reprinted from Leischner et al., Fluid inclusions and organic maturity parameters as
callibration tools in basin modelling, NPF Spec Publ 3, 1993, pp 161-172, with kind per-
mission from Elsevier Science - NL, Sara Burgerhartstraat 25, 1055 KV Amsterdam, The
Netherlands)
Fig. 2.26. Vitrinite reflectance values measured in well F by Leischner (1994; gray squares) and
by Teichmiiller et al. (1984; black circles). (Reprinted from Fortschr Geol Rheinl Westfalen, 32,
Teichmiiller et al., Inkohlung und Erdgas - eine neue Inkohlungskarte der Karbonoberflaeche
in Nordwestdeutschland, pp 11-24, 1984 with kind permission from Elsevier Science - NL,
Sara Burgerhartstraat 25, 1055 KV Amsterdam, The Netherlands)
120 M.N. Yal~m et al.
1400 ...-- - - -- - - - - . -O
=-- - - -:;:Tc:::
em =p=e=ra""'tu=
reC":d-=er:;:';v=ed:;--'1
1600
1.85 R. % ..... Vitrinite reflectance
1800 values determined at
this depth
~ 2000
.s 2200
:I:
1.05 Ro %.....o
Fig. 2.27. Maximum temperatures derived from fluid inclusions versus depth for well F. The
corresponding vitrinite reflectance values for the examined samples are included. (Leischner
et al. 1993)
Thermal History of Sedimentary Basins 121
• location ot well F
~""
.
Upper Jurassic
bib d I
[ ] Iso-rel/ectance
Contours (R %)
Q2> on tield . as noun ar es TopCarbonlPerous
Fig. 2.28. The Lower Saxony Basin and the location of well F. The intrusive complex of
Bramsche and accompanying intrusive bodies are outlined by the isorefiectance lines.
(Reprinted from Leischner et aI., Fluid inclusions and organic maturity parameters as calli-
bration tools in basin modelling, NPF Spec Publ 3, 1993, pp 161-172, with kind permission
from Elsevier Science - NL, Sara Burgerhartstraat 25, 1055 KV Amsterdam, The Netherlands)
§:
J::
0.
Q)
Cl
0.5 1.0 1.5 2.0 2.5 0.00.5 1.0 1.52.0 2.5 3.0
%R. %R,
::l Vitrinite rellectance calculated
u..
::c o Vitrinite rellectance (measured values)
o Vltnnite rellectance (TEICHMULLER et al. 1984)
300 275 250 225 200 175 150 125 100 75 50 25 0
and calculated vitrinite reflectance values. The temperatures indicated on the burial history diagram are the tem- :;
peratures derived from fluid inclusions. They do not agree with the isotherms constructed after the calibration with ~
TTl method. (Leischner 1994) ~
;f
f!>
3a
::c
t,;;.
o
-.';,l
rez. o.....
(/l
f!>
0.-
3'
f!>
::;
or
o -.';,l
tl:l
'"'"
;.
'"
I.c
li
Ql
o
0.5 1.0 1.5 2.0 2.5 0.0 0.5 1.0 1.5 2.0 2.5 3.0
%R, %Ro
::>
Ii. Vitrinite reflec tance calculated
I
~,05t> . . . ; :::... . .. fl Vitrinite reflectance (measured vatues)
, ; I r i I I
300 275 250 225 200 175 150 125 100 75 50 25 0 o Vltnnite reflectance (TEICHMULLER et al. 1984)
Time (Mabp)
Fig, 2,30. Recalibrated temperature history for well F using the paleotemperatures determined by fluid inclusion and the
IV
V.)
EasyO/O-Ro approach. (Leischner 1994)
-
124 M.N. Yal~m et al.
Table 2.6. Comparison of measured and calculated thickness and porosity values of individual
layers of the well in the Haltenbanken area
27QUAlERN
900
26U·PUOCB
•
15 U·MlOCENE
-..
18001 22 U·EOCI!NE
8 11 M·l.-I!OCENB
'-"
.sc..
to
Q 2700 1 16 CAMPANIAN
15SANT·nJR
14<l!NOMAN
3600 -l 1J ALBIAN
s::
-~ '-' '
SBAlO-AAU! .. ~
~-..-. ><
4TOAIlCW'I
- -... , '" eo.
-<">
lPIJENSBAC S
~
4S00 -i lSINll-IlBTI ~:) ~
1 IU\AF:JlAN
\
Thermal History of Sedimentary Basins 127
Table 2.7. Comparison of measured and calculated thickness and porosity values of individual
layers of the well in the Haltenbanken area after the adjustment of porosity values after the
first simulation
Fig. 2.31. Calculated (lines) vs. measured (dots) temperature and maturity values of the well in
the Haltenbanken area. Notice high maturity values at greater depths and a greater total
thickness which indicate an unsuccessful simulation
Well: North Sea Time: Present
Depth Plot N
00
Vitrinite Reflectance (% Ro) / Tn
-
Temperature eC)
Event 0 40 80 120 160 0.0 0.4 0.8 1.2
27 QVIIlllIIN
DE
900 26 V.I'LIOCENB
•
25 V·MIOCBNB
15 SAN'r·TUR
14CBNOMAN
13 A1.Il.1AN
3600 ~ S BAlG.AAl..I!
s::
~
4TOARClAN
-<
3 Pl..lENSBAC e:..
-(")
5
lS[N2.HBTr ~
4500 -l 1 RHABI1AN ~
Thermal History of Sedimentary Basins 129
To obtain a better fit to maturity parameters the heat flux values must be
decreased. However, this would result in a mismatch between calculated and
measured temperature values which are in a good agreement. As thermal
equilibrium requires a relatively short time, the present temperature trend
observed in the well can be simulated with an appropriate heat flux value per-
sisting only during the last few million years. Consequently the respective value
of the last event is retained and the heat flux values of all events except the last
one are decreased by 0.1 HFU. This abrupt increase in heat flow during the last
2 Ma has been required by almost all maturation models in the North Sea (see
Jensen and Don~ 1993). Since other indications of tectonism are unrecognized,
transient conditions caused by glaciation, overpressuring and fluid flow, which
cannot be handled completely and accurately by the existing modeling algo-
rithms, are considered as the most probable for conditions requiring an arbi-
trary increase in heat flux (Yal'rlll 1991; Jensen and Dore 1993). The adjusted
input data given in Table 2.8 led to a successful match, as shown in Fig. 2.33.
Table 2.8. Calibrated Input data of the well in the Haltenbanken area
Event no., name Lithology End-begin Thickness Porosity Water SWI Heat
(Mabp) (m) (%) depth temp. flow
(m) (DC) (HFU)
...
Fig. 2.32. Results of simulation with corrrected porosities. The total thickness is now
acceptable. However, maturities are still too high
Well: North Sea Time: Present
Depth Plot
w
-o
Temperature (Oe) Vitrinite Reflectance (% Ro) / TTl
Event 0 40 80 120 160 0.0 0.4 0.8 1.2
0
rlQUAllWI
900
26 U·PUOCENB
25 U·MlOCENB
1300 21 U·1lOCI!NB
,.-..
S
'-"'
i 21 M·L-IlOCENE
oS
0..
Q)
2700 i 16CAMPANlAN
0
IS SANT-1lJR.
14CENOMAN
13ALBlAN
3600 i S 8fJQ.AALl!
s::
;z
4 TOARCiAN ><:
!!'..
-(")
3PUl!NSBAC
5
~
4500 -l 2 SlIfl!.llEIT
IRHABI1AN ~
Thermal History of Sedimentary Basins 131
2.6
Thermal History of Sedimentary Basins: Case Histories
Thermal histories of six basins are presented below to demonstrate and em-
phasize the close relationship between different parameters and effects of the
dynamics of basin evolution to thermal history. For this purpose usually one or
two wells or a cross section from each basin are simulated. Only the final
results, that is, results achieved with a previously calibrated conceptual model,
are presented. The selected basins are:
- Cambay Basin, India
- San Joaquin Basin, California, USA
- Adana Basin, Turkey
- Styrian Basin, Austria
- Zonguldak Basin, Turkey
- Northwest German Basin
For each basin the geological history and differentiation of events, followed
by the input data used for the simulation, are briefly presented. Critical and
interesting aspects of the simulated temperature history are then discussed in
the light of the relevant parameters of the conceptual model. Most of the
examples are taken from published studies.
2.6.1
Cambay Basin, India
Fig. 2.33. Results of simulation with an adjusted heat flow trend. The match between mea-
sured and calculated values are now acceptable, for example, the simulation is successful
132 M.N. YalyIn et al.
71' .".
...
,-_==-_=,s"""
~
v v v v DeccIII Tnp
•• • Cntaceoaa
• • • • SediIIaItI
Fig, 2.34. Location map of the Cambay Basin. (Yalpn et al. 1988). (Reprinted from Kumar,
Ruby K, Dwivedi P, Banerjee V, Gupta V (eds), Petroleum geochemistry and exploration in
Afro-Asian region - proceedings of the first international conference, Dehra Dun, India, 25-27
November 1985, 1987, 558 pp., A.A. Balkema, P.O. Box 1675, Rotterdam, The Netherlands)
Babaguru, Kand, and Jhagadia Formations above the Tarapur Shale during
early and middle Miocene. Babaguru and Jhagadia Formations are arenaceous
and Kand and Kathana Formations argillaceous. This deposition was followed
by another break in sedimentation during late Miocene. During Pliocene and
Thermal History of Sedimentary Basins l33
thereafter the entire basin received sediments under marine and brackish water
conditions (Broach Formation). Quaternary sediments of Jambusar Formation
and the Gujarat Alluvium are the youngest units in the basin.
The entire sedimentary sequence was subdivided into 18 units: 15
chronostratigraphic (depositional) and 3 geochronological (erosional and/or
nondepositional) units (Fig. 2.35). Lateral lithofacies changes are common in
almost all depositional units. Fifteen different types of lithologies have been
distinguished in terms of sand, shale, and coal ratios. The lithological com-
position of each unit is also shown in Fig. 2.35. Maximum thickness of the
units and estimated water depths and sea bottom temperatures are listed in
Table 2.9. Heat flux density was determined as constant and uniform at 1.1-
1.3 HFU except for small areas where an increase of up to 1.7 HFU was in-
dicated.
Some interesting aspects of the thermal history of the Cambay Basin are be
explained below using time-temperature diagrams of selected units at one site
located in the Broach depression (Fig. 2.34). The temperature course of Olpad,
Cambay Shale I, and Kalol Formations at this point are analyzed. Immediately
after its deposition the Olpad Formation reached a temperature of about 175°C
at the base because of a very high sedimentation rate and rapid burial. During
the next 4 Ma cooling took place due to uplift and nondeposition. Deposition
of Cambay Shale units I-V (events 3-7) caused a rapid temperature increase
(Reprinted from Kumar, Ruby K, Dwivedi P, Banerjee V, Gupta V (eds), Petroleum geo-
chemistry and exploration in Afro-Asian region - proceedings of the first international
conference, Dehra Dun, India, 25-27 November 1985, 1987,558 pp., -. A.A. Balkema, P.O. Box
1675, Rotterdam, The Netherlands)
'1eIatocene
Jambuaar Fm. 4 8 14 6 6 Vol
-
Legend: ...
3 sandy shale
4 shale
5 shaly sand
6 sandstone
14 sand & shale
21 sandy shaly coal
22 shaly sandy coal
23 shaly coaly sandstone
24 coaly shaly sandstone
25 coaly sandy shale
26 sandy coaly shale
27 sand & coal & shale
29 sandy shale as trapwash
30 sand & shale as trapwash
31 shaly sand as trapwash
/~ erosion
Tarap&ar Sh.
4 8 14 15
. I 'I
"
~ hiatus
- 1(&101 Fm.
.!! 4 8 14 6 24 116 It 15 8 4
Eooene I :g • • ,.
~ 4~21=22=23:24=25_28_21 _ _ • _ _ 5·4_14 '4:'-4:
.. '" . , 3,5,14,21,24,25,26.27.27
"
~
""' CambaySh.1 8 4 8 4
w
1~luncon~rml~112~~~~~~~~~~~~~ ~
Paleocene. . J Olpad Fm. 1 4 81 21 4 81 a ao 4 81
~
Deccan Trap
><
e'-
-<"l
Fig. 2.35. Time-rock synopsis of Cambay Basin. (Yalpn et aI. 1988). (Reprinted from Kumar, Ruby K, Dwivedi P, Banerjee V, Gupta V 5
~
(eds), Petroleum geochemistry and exploration in Afro-Asian region - proceedings of the first international conference, Dehra Dun,
India, 25-27 November 1985, 1987, 558 pp., A.A. Balkema, P.O. Box 1675, Rotterdam, The Netherlands) ~
Thermal History of Sedimentary Basins 135
10
14
, I
I
/
13 /
/
/
12 I
I
20
11 I
,I
,
10 ,,,
,,
30
I
I
I
I
9
I
40
I
I
8
::::7
:::: 654_
=
,= .' .
..
50 _
3 --OlpadFm.
. ... Cam bay Sh.l .
2 - - - Kalol Fm.
60 1
Fig_ 2.36. Temporal development of temperature in the Olpad formation, Cambay shale I, and
Kalol formation at point A in Broach depression. (Reprinted from Kumar, Ruby K, Dwivedi P,
Banerjee V, Gupta V (eds), Petroleum geochemistry and exploration in Afro-Asian region -
proceedings of the first international conference, Dehra Dun, India, 25-27 November 1985,
1987, 558 pp., -. A.A. Balkema, P.O. Box 1675, Rotterdam, The Netherlands)
both in Olpad Formation and in the Cambay Shale I (Fig. 2.36)_ The rapid
increases are related to relatively high sedimentation rates and rapid burial.
The deposition of the Kalol Formation caused only a slight temperature in-
crease, whereas the deposition of the Tarapur shale (event 9) resulted in a
slight decrease in temperature in spite of a deposition of nearly 1000 m. The
reason for this unusual cooling effect is the extremely low sea bottom tem-
136 M.N. Yal~m et al.
2.6.2
San Joaquin Basin, California, USA
The San Joaquin Basin is located in the southern extension of the Great Valley
in California (Fig. 2.37). The Great Valley sediments were deposited in a
forearc basin between a trench in the west and a magmatic arc in the east.
Deposition in the San Joaquin Basin started with Upper Cretaceous (Santo-
nian) sediments. The growth of the forearc basin continued into the Campa-
nian and led to the accumulation of several thousand feet of submarine fan
deposits (Forbes, Sacremento, and Lathrop Formations). Very fast deposition
and rapid progradation to the west caused a filling up of the basin and a
gradual replacement of the deep marine sedimentation by slope and shelf
deposition during late Campanian and Maastrichtian (Sawtooth, Tracy-Star-
key, Ragged Valley, Blewet, and Moreno Formations). By the end of Cretaceous
the forearc basin was almost completely filled. Consequently Paleocene Garzas
Sandstone and Lodo Formations are shallow marine deposits. The truncation
of the Paleocene units at the base of Middle Eocene Domengine sands indicates
uplift and erosion during early Eocene. Regional subsidence at the beginning of
late Eocene caused an extensive marine transgression resulting in the de-
position of marine shaly lithologies of the Kreyenhagen Formation until the
end of early Oligocene. Late Oligocene was an erosional period in the northern
part of the basin. The deposition during the last 20 Ma was strongly controlled
by the movement of the San Andreas transform fault system and related
wrench tectonism. During this period mainly shallow marine to nonmarine
units (Vaqueros, Temblor, St. Margarita, McLure and Tulare Formations) were
deposited. Only in the southernmost part of the basin is Lower Miocene rep-
resented by deep to moderately deep marine units. The time-rock synopsis
Fig. 2.37. Location map of San Joaquin Basin. (Welte et al. 1985)
- - -
Oregon
-Caiiior~ -- - --,
area 0 f 3- D simulation
,
Redman-SIOT~
\ ",
s. ~~ chowc~illa
<!l~ 0
Shaw
oSooza
0
Gill
0 Young
" ,
porte:;!8SF:'"alman - \
OOJ~
"".~"~
"1.n 0
Westhaven
~(",. .
~" oDaniel
~
• Bakersfield
o 100km
t
?'f)7$ ~~rbeds
ovep
/-
~
Older beds
eroded
nonmarine
deposition +++ Basement
+ +
Kreyenhagen 2 15
~
Oligocene
to Kreyenhagen Kreyenhagen I 14
Eocene
ND+Santonian
+ + ~--.-~-~~--+-+-+-+-+-+,...,.,.;--++-+ ,,+-+-""'!"'-~
...
+ + +++++++++++
Thermal History of Sedimentary Basins 139
summarizes the stratigraphic evolution and shows the absolute geological time
of different units (Fig. 2.38).
Twenty events were distinguished. Eighteen of these are depositional, and
lateral lithofacies changes are common within them. A wide spectrum of clastic
rocks ranging from shale and siltstone to coarse sandstone define the litho-
types. Estimates of paleowater depths and sea floor/surface temperatures are
shown in Table 2.10. Considering the geological history and the basin type a
relatively low and constant heat flow value of 1.10 HFU (Fig. 2.39), typical for
forearc basins, was used which gave good agreement between calculated and
observed calibration parameters in all the wells at the western flank of the
basin. However, simulation of the key wells at the eastern flank showed that the
constant and low heat flow values did not lead to an acceptable match. Further
calibration and sensitivity tests indicated that the heat flow values must have
been much higher than 1.10 HFU in the geological past and lower during
recent times. Values up to 1.6 HFU in the past and 0.90 HFU in more recent
periods were determined (Fig. 2.39). Such high heat flow values are likely
caused by magmatic or volcanic events. However, there is no evidence of such
events at the surface or within the sequence. Therefore deep seated magmatic
bodies which probably formed in connection with the Sierra Neveda magmatic
arc are postulated. Evidence for such intrusions is detected on the gravity map
Fig. 2.38. Time-rock synopsis of the northern part of the San Joaquin Basin
140 M.N. Yalpn et al.
A. Heat Flow between 88.0 and 7.0 Mabp B. Heat Flow between 7.0 Mabp and present
SCAlE
o 10 20
I "" ,
Fig. 2.39. Changes in heat flow with time in San Joaquin basin. The drastic changes at 7 Mabp
are due to the effect of the San Andreas fault. (Welte 1989)
of the basin as positive gravity anamolies which coincide with areas of past
high heat flow. Furthermore, the time of the rapid heat flow decrease coincides
with the abrupt change in the crustal configuration at about 7-8 Mabp caused
by the northward migration of the Mendocino triple junction which converted
the subduction margin into a transform margin. Consequently subduction,
associated magmatic activity, and the high heat flux in the sedimentary se-
quence ceased.
Thermal History of Sedimentary Basins 141
Temperature
Sediment ! Water Sedimentation
Heat flow (HFU) interface (0C) rate (m ! MA) Temperature (0C)
E4Jenl Utho
NO ",peO 0.5 1.0 a 5 10 15 a lOa 300 50
0 o
20 36
19 36
10 18 36
10
17 36
20 16 36 20
15 4
30 30
a:
D
14 4
~ 40 40
<0
E
F 50 13 6
50
12 36
11 38
60 10 33 60
9 4
8 5
70 7
.6
10
3 70
5 32
4 3
80 3 11
2 3 80
1 33
90 90
Fig. 2.40. Temporal distribution of heat flow, sediment/water interface temperature, sedi-
mentation rate, and temperature of the layer Santonian at point A. (See Fig. 2.39 for the
location of point A)
Using this heat flow configuration and other data the thermal history of the
San Joaquin Basin was reconstructed as a three-dimensional study (Welte et al.
1985). General trends of the thermal history are demonstrated here with the
help of the relevant input data and the temperature-time curves of the San-
tonian at two selected grid points A and B (Fig. 2.39). Point A is located in the
western part of the basin, where the heat flow remained constant at its initial
value of 1.10 HFU (Fig. 2.40). Point B is located in a basin area with a higher
heat flow of 1.20 HFU until 7 Mabp, after which it was reduced to 1.00 HFU
due to the above mentioned changes from a subduction into a transform
margin (Fig. 2.41). The temperature-time curves of Santonian at these points
indicate clearly that major increases in temperature are controlled by the rapid
deposition of Lathrop and Blewett/Moreno formations (events 4 and 8). At
point A even with the slightly lower heat flow than point B, higher tempera-
tures are reached because Santonian was buried deeper at this point by Lathrop
and Blewett/Moreno formations. At point A as a consequence of this rapid
increase the temperature at the base of Santonian started to drop at 60 Mabp
142 M.N. Yalpn et al.
TEMPERATURE
_lIIho.HEAT FLOW
SEDIMENT I WATER SEDIMENTATION
(HFU) INTERFACE ("C) RATE (nv'MA) TEMPERATURE (OC)
1'b ....,. 0 Q.6 1.0 ~ 10 16 o 100 2IJ) ;lIJ) CXl /OJ 0 /ill 100 1~
L
0 0
2D
19
:16
:16 J (
10 11 :16 1o
11 :16 ]
20 16 :16 20
30
15 • r- 30
Ia. «l 1.
•
w
::Ii
~
50 IS 6 50
I?
12 M
)
11 M
60 60
10 s:I
9
I
•5
h
70 1 10 70
(
6 S
5 S2
4 3
(K) 3 11 80
2 3
90
I s:I
I 90
Fig. 2.41. Temporal distribution of heat flow, sediment/water interface temperature, sedi-
mentation rate, and temperature of the layer Santonian at point B. (See Fig. 2.39 for the
location of point B)
although burial was continuing and SWI temperatures and heat flow were
remaining unchanged (Fig. 2.40). At point B cooling started as expected 5 Ma
later, that is at 55 Mabp, when an uplift and erosion took place (Fig. 2.41).
Thereafter temperatures of the Santonian remained more or less constant until
the period of regional heat flow decrease at 7 Mabp, which caused a slight drop
in temperature at point B (Fig. 2.41). At point A, where the heat flow remained
unchanged, temperature increased slightly, as expected (Fig. 2.40). Other de-
tails of the thermal history of the San Joaquin Basin are given by Welte et al.
{l985), Yalpn and Welte (1988), Welte and Yalpn {l988) and Welte {l989).
2.6.3
Adana Basin, Turkey
The Adana Basin is located in southern Turkey between the Taurus Mountains
in the north and Cyprus in the south (Fig. 2.42). The basin formation was
Thermal History of Sedimentary Basins 143
N
t
D~
. ~
~~~
0
,
30
4
60
•
90,
Ir:m
2
:W
2
17
3 3
16
4 4
15
5 5
13
6 6
7 7
~
~ 8 10 8
e9 :~:
9
~10 7 10
i= 11 6 11
12 12
13 4 13
14 3 14
15 2 15
16 16
17 17
18 ~t--;--,,--r-~-r-;~r-~-'~~--r-r-'-~~'-~~-'--r-'--r~ 18
Fig. 2.43. Sedimentation rate, sediment/water interface temperatures, heat flow, and tem-
perature history of the lowermost unit in the Kuransa well
0
Q)
--....
0
til
1000
-
::l
CJ)
C
Q)
E 2000
"0
Q)
CJ)
0
~ 3000
Q5
.c
E""-""
4000
::r:
~
a..
w 5000 60--lsotherms (0C)
0
6000
20 18 16 14 12 10 8 6 4 2 0
TIME (Mabp)
Fig. 2.44. Burial history diagram of the Kuransa well in Adana Basin with isotherms showing
the temperature development as function of time and space
Thermal History of Sedimentary Basins 145
from the sediment surface. Figure 2.44 shows that not only the lowermost unit
in the well but the entire sequence was effected by the deposition of evaporites.
Although temperatures increased slightly during this period, the geothermal
gradient decreased, as indicated by dipping of isotherms. The change in the
geothermal gradient both as a function of time and depth is a good indication
of basin dynamics. Details of the temperature history of the Adana Basin are
presented by Yalpn (1988, 1990, 1991).
2.6.4
Styrian Basin, Austria
The more than 4-km-deep Neogene Styrian Basin is located at the eastern
margin of the Alps and forms part of the Pannonian Basin System (Fig. 2.45). It
•
N
10km
I
1-----1
fOl Plio-lPlelstocene
~ volcanic rocks
Fig. 2.45. Position of the Styrian Basin within the Alpine-Carpathian-Pannonian region and
sketch map of the Styrian Basin with location of volcanic rocks (Sachsenhofer 1994). I, II, III,
Cross sections discussed in the text. A subeconomic gas deposit was detected in the Lu-
dersdorf-Wollsdorfregion. Ii, Litzelsdorf 1; S, Stegersbach 1; Wa, Waltersdorf 1; Bl, Blumau
1, la; F, Fiirstenfeld 1; U, Ubersbach 1; B, Binderberg 1; J, Jennersdorf 1; W, Walkerdorf 1; Wo,
Wollsdorf 1; L, Ludersdorf2; M, Mitterlabilll; N, St. Nikolai 1,2; P, Perbersdorf 1; Pi, Pichla 1;
Mu, Mureck 1
146 M.N. Yal~1ll et al.
m ybp
Subsidence
hista<y (lcml
Subsidence rates
(emil 00,.1
Tectonic
regime
I Sea IEweI
changes
I Depositionol
environment
Magnatic
evenls
2 4 10 20 11CNtjiJ.
o
regre~ .
o
I Pleistocene
~ ROI'I"oOOon
~
Basalis
Q)
%
II0: Dazb1
/
5 5
Pon1krl
.S1 ~ fluviatile-
.9 ~
r-----
Ilmnlc
!
~
10 I'cnncrlOn Q) 10
£"
Q)
~
c:
Q)
SamotIoo
~ blaekish
u ~
15
iE :E
l·
M.·
~
marine 15
E· Andesites
0Ip01I0n
l---r-
?/finn
~ extenliorI
p.AI oP01'l
~
~
~ ggen-
20 tuglon 20
Fig. 2.46. Summary of the Neogene evolution of the Styrian Basin (Ebner and Sachsenhofer
1995). The geological time scale follows Steininger et al. (1990). {Reprinted from Tectophysics,
242 (1-2), 133-150, Ebner F, Sachsenhofer RF, Paleogeography, subsidence and thermal
history of the Neogene Styrian Basin (Pannonian basin system, Austria) 1995, with kind
permission from Elsevier Science - NL, Sara Burgerhartstraat 25, 1055 KV Amsterdam, The
Netherlands)
Thermal History of Sedimentary Basins 147
slopes of volcanic islands during early and middle Badenian times. In Pliocene
times a basin inversion resulted in the erosion of a few hundred meters of
sediment. Uplift was accompanied by a second volcanic phase producing ba-
salts in Plio-/Pleistocene times.
The evolution of the Styrian Basin and the reconstruction of the thermal
history were studied in five individual wells and along two cross sections (I, II;
Fig. 2.45) using a two-dimensional finite-element software system. Hydro-
carbon migration was studied along a third cross section (III; see Chap. 7, this
Vol.). A relatively complex geological evolution and periods of volcanic ac-
tivity, influenced the temporal and spatial distribution of heat flow sub-
stantially. Therefore a careful calibration of the heat flow history was necessary.
The heat flow evolution along cross section II which crosses a Karpatian
(Nikolai) and an early Badenian (Mitterlabill) volcano are discussed here as an
example (Fig. 2.47a). A total of 30 events and 50 gridpoints including 5 cali-
bration wells were used to define the geological model. Several calibration runs
were necessary to reach a fit between measured and calculated data, which are
presented in Fig. 2.49. The temporal and spatial distribution of the heat flow is
shown in Fig. 2.47b. The simulation of the basin evolution with this heat flow
N s
B
3 ~~------------~~~L-------------------~
8 ottnonglan (3-5)
BadeniOn (13-15)
Karpatian (6-12)
Sarmation (16-17)
300
E
1200
3:
g
'§ 100
:::c
o (b)
o 5 10 15 20 25 30km
Fig. 2.47.a Stratigraphy along cross section II with position of calibration wells. M, Mitter-
lab ill; N, St. Nikolai; P, Perbersdorf; Pi, Pichla. b Heat flow model applied to cross section II
(Sachsenhofer 1994)
148 M.N. Yal~m et al.
N s
Ml 2 N 1 Pl Pll
Oi===-===-
Fig. 2.48. Calculated temperature distribution along cross section II for Karpatian (a) and
early Badenian times (b). 5.1., Sea level. (Sachsenhofer 1994)
data enabled the reconstruction of thermal evolution along the cross section.
The calculated temperature distribution during Karpatian and early Badenian
is shown in Fig. 2.48. The great effect of the volcanic activity on the heat flow
pattern and the resulting temperature distributions are shown in Figs. 2.47 and
2.48. The Karpatian heat flow was extremely elevated in vicinity of the Kar-
patian (Nikolai) volcano resulting in an up doming of the isotherms. In con-
formity with moving magmatic activity, the heat flow maximum was shifted
northward to the Mitterlabill area, which became a center of volcanic activity in
early Badenian times. A good fit between measured and calculated vitrinite
reflectance data in this area can be established only assuming extremely high
heat flow (330 mW/m2) and erosion of 400-450 m thick early Badenian an-
desitic rocks. Determination of the exact values of heat flow and erosion, which
are necessary to establish a good fit, also depends on the physical properties
(particularly thermal conductivities) of the eroded rocks. These parameters
cannot be measured. Furthermore, the eroded thickness would be over-
estimated if heat is transfered from the nearby volcanic vent or from the
overlying andesites laterally and with resulting enhancement of vitrinite re-
flectance in shallow Karpatian sediments below the andesites. In any case the
erosion of thick andesitic rocks (and the shallow water depth of the Badenian
Thermal History of Sedimentary Basins 149
,
kin
B J
S t B •
B ~
B l
K i~
K
S
1"1
Sormotlon
~
2
0
" B
K
Bodenion
Karpa1ian
~
• measured
calculated
0 otInangion
CJ Volcanic
rocks
3
(b) Pichla 1
Temp. Vitr. Ren. Sterone Hopone Steroid Oil Pot.
(0C) (%) lsomenz. lsomeriz. Atom . (gHC/gTOC]
0 100 0 20 0.3 0 0 3. 5 0 0.5 0 0.1 0.2
kin
Fig. 2.49. a Comparison of measured and calculated vitrinite reflectance data of four wells
along cross section II. b Comparison of measured and calculated temperature data and ma-
turity parameters (vitrinite reflectance, sterane isomerization, hopane isomerization, steroid
aromatization) of the Pichla I well. Oil potential has been calculated using kinetic parameters
for Karpatian sediments (Sachsenhofer 1994)
Sea) indicate that the Mitterlabill volcano must have been raised significantly
(500 m) above the early Badenian sea level (Fig. 2.48b). Erosion occurred
during the middle Badenian, which is represented by a stratigraphic gap in the
Mitterlabill 1 well. After the end of the magmatic activity heat flow decreased
along the whole cross section and has been 55-85 m W1m2 since late Sarmatian
times.
150 M.N. Yal~m et al.
,£ PIeisb:.
-- Plchlo.1
OJ ----- MltIeI1abili 1
cQ) Romcr/on • .• . .. Blumou 1.10 BasaltS
r--- -- Ubersbach 1
~ 0azJ0n
5 a: 5
Ponb1
Q) -
§
10 PavlonIon 10
Q)
c
Q)
()
ScIfrra1b1
OQ) - C
-'5 L- .Q .. .... ...... ...
:E.l2 M.- ~
15 :E 1---------~;--; 15
E.- £ : I Andesites
1fapob1
~~
~ ?
~Eggeo- ?
20 blIgon 20
Fig. 2.50. Heat flow history of the Styrian Basin. Different lines indicate the heat flow evolution
of selected wells_ Pichla 1, Mitterlabill 1, and Blumau 1, la wells are situated in vicinity of
Miocene volcanoes. (Modified after Sachsenhofer 1994)
The heat flow history of the Styrian Basin is summarized in Fig. 2.50. Ex-
tremely elevated heat flows during Karpatian to Badenian times are most
probably a consequence of shallow magma chambers. In the southern part of
the basin (e.g., Pichla area), heat flow decreased immediately after the Kar-
patian, whereas it remained high until early or even middle Badenian times
near the Mitterlabill well and close to the northeastern volcano (e.g., Blumau
area). This is a consequence of northward shifting of magmatic activity. In the
PichI a area heat flow decreased immediately after the end of magmatic activity
whereas in the Blumau area this decrease took place 1 Ma after the end of
magmatic activity. This difference may indicate the presence of a larger magma
chamber below the northeastern volcano, which required a longer time to cool
down. Modeling showed that the effect of raised heat flow in vicinity of the
volcanoes disappeared at a distance of about 10 km and heat flow approached
background values of about 120 mW/m2 (Fig. 2.47b). Since late Sarmatian,
heat flow along the entire cross section has been generally in the range of 55-
85 mW/m 2. This relatively high heat flow is probably due to a thinned crust
beneath the Styrian Basin. Namely, present thickness of the crust is about 25-
30 km (Aric et al. 1987). Present formation temperatures in some wells in the
Thermal History of Sedimentary Basins 151
..
'
..
I
'
32'00'E .......
.. '
AMASRA
" =+
B:~EA
-+-- - - '----:~--I_--
.
,
41 30 N
~ Carboniferous
Outcrops
... Modelled wells
Ak-7
.....2oom·..Isobathymetric lines
Scale
o 10 20km
Fig. 2.51. Location map of the Zonguldak Basin also showing sites of the modeled wells
easternmost part of the basin indicate a slight heat flow increase (5-10 mW/m 2 )
during Pliocene or Pleistocene. Whether this is a consequence of hydro-
dynamic effects or due to Plio-/Pleistocene basaltic volcanism is yet not known.
In any case this latter volcanic phase had only little effect on regional heat flow
patterns. Perhaps this is a result of the great depth of the relevant magma
chambers (50-80 km; Kurat et al. 1980). More details of the thermal history of
the Styrian Basin are given by Sachsenhofer (1994).
2.6.5
Zonguldak Basin, Turkey
The Zonguldak Basin which is located in northwestern Turkey on the Black Sea
coast (Fig. 2.51) is formed on a Hercynian continental sliver (Okay et al. 1994).
Basin development started at the end of Visean when a carbonate platform was
converted in to a deltaic basin due to a tectonic uplift to the north. Deposition
started with prodelta Namurian sediments which were followed by a pro-
gradational Westphalian sequence of delta-plain sediments which include coal
seams. At the end of Westphalian the entire basin was uplifted and eroded.
Continental clastics in the eastern part of the basin represent a new deposi-
tional period which commenced in late Permian and continued until middle
Liassic. After a second period of uplift and erosion the basin area was flooded
by a shallow sea during early MaIm and platform-type carbonates were de-
posited. The formation of the Black Sea Basin as an extensional back-arc basin
152 M.N. YalyIn et al.
i8
50 ·17
16
111
14
100 111
.... ~L
. Jr·
a. 150 8
.0
>-
E 7
200
~
t-
II
II
1----~
Temperature
CC)
40 40 80 120 160 200
00
50
100
...... 150
ClIO.
E.o
.- >-
I- .....
E 200
300
350
Thermal History of Sedimentary Basins 155
2.6.6
Northwest German Basin
•
Fig. 2.53. The temperal distribution of sedimentation rate, water depth, sediment/water in-
terface temperature, and heat flow which are used for the modeling of the well Ak-7 as input
Fig. 2.54. Temperature vs. time diagrams of the Namurian Alacaagzi formation in the modeled
wells
156 M.N. Yalpn et al.
230
II
Volcanisms
275
Inor Reservoir
350
Devonian
405
Silurian
440
Fig. 2.55. Schematic lithological and stratigraphic column for the study area with major gas
source and reservoir rocks and some important tectonic events. (Modified after Barnard and
Cooper 1983)
which led to very high heat flows (up to 150-200 mW/m2) there. For the south,
lower heat flows (but still above the crustal average of 60 mW/m2) are thought
to have persisted during the Autunian. Therefore the early Permian is regarded
as the time of first gas generation from the Carboniferous source rocks along
the entire profile, but it is thought that the rate of gas generation was much
higher in the north than in the south. This expectation is due not only to the
greater heat flows in the north but also to the greater burial depth (Fig. 2.57).
-l
40 o .60 .70 .80 ::r
3'"e:..
lOOO~ 46 ::r:
c;;.
0-
~
o-.
en
p.
'"
[3 '
;:t
'"
'"
~
t>:l
'"
'"5 '
'"
-£i 6000
0..
~
o
420·450
450·480
Fig. 2.56. General stratigraphy and temperature along a north/south profile in northwest Germany. The transect is about 100 km long and
V1
situated south of Hamburg
"
......
U1
Time (my) ex>
50 . 0
~\ ~ ?31 ~ ~
1000
2000
3'000
4000
r-.. 5000
E
'-'
-S 6000
0-
0
Cl 7000
8000
9000
1000
2:::
Z
110001 I·
>-<
~
..n
120001 5
~
~
Fig. 2.57. Burial histories for two sites in the northern (a) and southern (b) part of the transect shown in Fig. 2.56. The relatively high heat
flows during the Autunian are due to assumed high heat flows in relation to the volcanic activity at that time
....,
Time (my) P""
(1)
aeo.
:os
'"0-
1000
~
o
C/)
"""
2000 (1)
0...
s-
(1)
3000 ::>
or
~
4000 tX
""'"~.
,--.. 5000
E
'-'
-5 SOOO
0-
(l)
a 1000
240·270
8000
270-300
9000 00-330
1000 330~360
V>
'-0
Fig.2.57b
-
160 M.N. Yal~m et al.
For the Mesozoic and Cenozoic times constant heat flows of about 60 mW/
m2 are thought to have persisted, although it can be argued that slightly ele-
vated heat flows may have occurred during some periods. There are, however,
no indications for very high heat flows; for example, there are no indications of
strong volcanic activity or rifting. Whether or not the North Sea rifting has
influenced the study area remains speculative at present. In any case organic
maturity parameters bear no imprint of any high temperature events during
the Mesozoic or Cenozoic but are a function of the Neogene heat flows and
burial depth. The present-day burial is the greatest which the sediments ex-
perienced, but the burial depth reached during the Jurassic was not much less
(Fig. 2.57). Therefore the Triassic/Jurassic is regarded as the second period of
gas generation and migration and the Cenozoic as the third period. More
details of the gas accumulation history are discussed in Chapter 7.
Present-day temperature profiles for several wells indicate that heat flows
have recently been slightly lower than 60 mW/m2 , and that average geothermal
gradients for the upper crust are in the range of 27 °C/km (Fig. 2.58). Not only
present-day temperatures but also vitrinite reflectance values are a function of
the present depth of burial, as shown in Fig. 2.58. In view of the fact that burial
depth during the Jurassic differed little from those at present, this observation
is regarded as an additional proof of low or average (but not high!) heat flows
during the Mesozoic. With the burial and heat flow history described above, it
was possible to obtain good fits between measured and calculated vitrinite
reflectance values.
One special aspect of the temperature simulation along the transect is the
temperature disturbance below and above salt domes (Fig. 2.56). Generally
2000 2000
3000 3000
4000 4000
5000 5000
Fig. 2.58. Plots of corrected present-day borehole temperatures (A) and vitrinite reflectance
values (B) versus depth for several wells in the study area. Symbols, various wells
Thermal History of Sedimentary Basins 161
temperatures below the salt domes are lower than typical for the respective
depth level, whereas those above the salt domes are higher. This phenomenon
is due to the high heat conductivity of salt compared to other lithologies. The
difference in temperature between areas directly below salt domes and those
adjacent to them may exceed 10°C for the uppermost Carboniferous units
according to the simulations (Neunzert et al. 1996). This difference would be
large enough to significantly reduce gas generation below the salt domes or, in
other words, to preserve a higher gas generation potential in the Carboniferous
units below the salt domes. Whether this temperature effect is as large as
calculated or smaller due to higher rates of lateral, possibly convective, heat
transfer remains to be tested in the future.
2.7
Concluding Remarks
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Chapter 3
Maturation and Petroleum Generation
Chapter 3: Overview and Insights
3.1
Introduction
It is now firmly established that crude oil and most natural gas, collectively
termed petroleum, are generated from kerogen in sedimentary source rocks.
The organic origin of crude oil is beyond doubt based on optical activity
(Oakwood et al. 1952; Hills and Whitehead 1966) and isotopic composition
(Silverman 1964). The chemical structure of biological markers in ancient
sediments and crude oils compared to that of living cell constituents (Calvin
1969; Albrecht and Ourisson 1971; Tegelaar et al. 1989a), and regularities in
crude oil composition according to sedimentary environments (Tissot and
Welte 1984) further confirm an organic origin. However, it was uncertain for a
long time at what depth petroleum forms in the earth. The discovery of hy-
drocarbons in Recent sediments by Smith (1952) gave support to a shallow
origin for oil. Baker (1960) and Meinschein (1961) noted that the amount of
hydrocarbons in Recent sediments could account for known oil reserves.
However, Stevens (1956) found only a few simple aromatic hydrocarbons in
Recent sediments as compared to the numerous complex aromatic hydro-
carbons in ancient sediments and crude oils. Other authors (Emery and
Hoggan 1958; Dunton and Hunt 1962; Hunt 1975) noted the abundance oflight
hydrocarbons (Ce Cl3 ) in petroleums and their absence in young sediments. It
was thus argued that petroleum must form at greater burial depths. Im-
portantly, Bray and Evans (1961) and later workers (Brooks and Smith 1967;
Leythaeuser and Welte 1969; Allan and Douglas 1977) observed that hydro-
carbon distributions gradually evolved in going from Recent sediments to
ancient sediments to crude oils, suggesting that the origin of crude oil is
irrefutably tied to the maturation of sedimentary organic matter. Owing to this
relationship, maturity assessments of petroleum source rocks and crude oils
are to be considered crucial in petroleum exploration studies (for a review, see
Brooks 1981).
lInstitut fUr Erdiil und Organische Geochemie (ICG-4), Forschungszentrum Jiilich GmbH,
52425 Jiilich, Germany
2 Institut fUr Chemie und Biologie des Meeres (ICBM), UniversiUit Oldenburg, Carl-von-Os-
sietzky-Str. 9-11, 26111 Oldenburg, Germany
3.2
Maturation: Definition and Driving Force
3.3
The Phenomenon of Petroleum Generation
3.4
Kerogen Maturation
3.4.1
Petrography: Vitrinite, Other Macerals, and Microscopic Approaches
3.4.2
Maturity-Related Changes of Optical Properties of Macerals
Upon maturation, vitrinites lose volatile products such as water, carbon di-
oxide, organic acids, and hydrocarbons (van Krevelen 1993; Littke et al. 1989).
These chemical changes are accompanied by changes of physical properties.
Most importantly, there is an increase in vitrinite reflectance which according
to the Fresnel-Beer equation (3.6) is a function of the absorption coefficient
(k), the refractive index of the vitrinite particle (n), and the refractive index of
the overlying medium (no; usually oil with no = 1.518; see Ting 1981 for more
details).
R = [(n - no)2 + n2 k2 ]/[(n + no)2 + n2 k2 ] (3.6)
The applicability of vitrinite reflectance as a maturity parameter predicting the
stage of oil and gas generation depends on the extent to which the decrease in
entropy of vitrinite due to loss of volatile products is correlated with the
decrease in entropy of liptinite, which is the major source of liquid hydro-
carbons. In nonisothermal heating experiments under ambient pressure this
correlation was bad because most petroleum generation from alginite took
place at temperatures clearly below those at which vitrinite reflectance started
Maturation and Petroleum Generation 177
"0
~ 1.0 ~ ~ ~ ~ El
>-
o
u::
~ 0.5 /6
o 4
~
U: 0 ~
o 0.5 1.0 1.5 2.0
Vitrinite Reflectance (%)
Fig. 3.1. Fraction of total FID yields (hydrocarbons and related substances) during pyrolysis of
vitrinite as a function of vitrinite reflectance at heating rates of 0.1 (solid lines) and 20°C/min
(dashed lines). (Reprinted from Schenk et aI., Structural modifications of vitrinite and alginite
concentrates during pyrolytic maturation at different heating rates. A combined infrared, l3 e
NMR and microscopial study. In: Durand B, Behar F (eds) Advances in organic geochemistry
1989. Pergamon Press, Oxford, 1990, pp 943-950, with kind permission from Elsevier Science
Ltd, The Boulevard, Langford Lane, Kidlington OX5 1GB, UK)
to increase (Fig. 3.1; Schenk et al. 1990). In contrast, case studies on alginite-
rich source rocks of the Kimmeridge Clay and Posidonia Shale formations
suggest that an excellent correlation does exist under geological conditions.
Certainly the onset of intense C1S + hydrocarbon generation was consistently
detected at 0.50%Rr despite variations in geothermal history among the study
areas (Radke and Willsch 1994). Thus heating experiments as those mentioned
above cannot serve as a model for the maturation of vitrinite in nature. The
observation that oil generation from type II kerogen generally starts at 0.5%Rr
and ends at 1.3%Rr does not mean that this must be true for all sedimentary
basins. High heating rates supposedly result in different reflectance-generation
relationships (Yalylll and Welte 1988; Mukhopadhyay 1992). Therefore geo-
logical information on burial and temperature history may help interpret vi-
trinite reflectance data to predict the state of oil generation correctly.
An additional problem is the fact that it is not yet known to what extent
factors other than time and temperature, such as host rock facies or pore fluids,
affect vitrinite reflectance during catagenesis. In comparison with depth-re-
flectance trends defined by measurements on coal samples, those determined
on vitrinite particles from clastic and carbonate rocks usually show the same
general trend but more scatter than in coals (Fig. 3.2). In most cases mean
vitrinite reflectance values measured on rocks of different petrographic com-
position but from the same narrow depth interval do not differ by more than
15% of the value and may be attributed to different botanical vitrinite pre-
cursors or early diagenetic processes (Buiskol Taxopeus 1983).
"Suppressions" of vitrinite reflectance in oil shales reported by Hutton and
Cook (1980) and other authors were attributed to an incorporation of bitumen
from external sources, i.e., from liptinites ubiquitously present in the oil shales.
However, as no significant difference in reflectance exists between data mea-
sured on extracted and nonextracted (bitumen-impregnated) specimens of the
same sample (Wenger and Baker 1987), this explanation seems to be pre-
178 M. Radke et al.
Vitrinite Reflectance, Rr (% )
0.5 0.7 0.9 1.1 1.3 1.5 1.7
1000
.
..
I!I'
-
°A A
A
,~ .0
Profile I
c.~ .0
U
1250 CD .~ B
950 ~t·CD
AA
..,. .A
I-
A A
Ai .~. A
o ,.
i, s'
AlJ.cA/A
IJo \ . Profile IT
N
III
.....§
Crf- •
'"a
~
8
D
... ...t::
a
-~
." [Jill
"-' 0" !"o
.;3
e-
oO~c'lr··. 0
. ..,
til
o •
III
0 1550
900
..
.. ..
• .be•
'
". ..
.to
p Profile III
~
.
~ A
A
• Coal Seam o ••
• Mudstone A,.
Fig. 3.2. Increase in mean random vitrinite reflectance (%Rr) with depth in three cores of
different maturity levels, all drilled in the northern part of the Ruhr area, Germany. Vertical
scale, depth of the sample in the individual core. The profiles are put together according to
their stratigraphic age. (Scheidt and Littke 1989)
mature. What is more important, Schenk et al. (1990) demonstrated that not
even the release of the bulk of volatile products from vitrinite upon pyrolysis at
300-350 °C significantly changes reflectivity. The reflectance increase above
350°C is due mainly to the rearrangement of aromatic units {Fig. 3.1}. Ac-
cordingly, differences between reflectance values of dispersed vitrinites in
clastic rocks are unlikely to depend on bitumen impregnation.
A different usage of reflectance data was initiated by basin history simula-
tions during the last two decades. Lopatin {1971} developed a mathematical
formalism describing maturity as an exponential function of temperature and a
linear function of time. Considering Lopatin's method, Waples (1980) in-
troduced the time-temperature index as a new maturity parameter. TTl values
were originally calibrated against measured vitrinite reflectance and thermal
Maturation and Petroleum Generation 179
alteration index values of 402 samples from 31 wells. According to this cali-
bration, a doubling of the rate of the chemical reactions involved in thermal
maturation with every 10°C rise in temperature was assumed. Slightly mod-
ified equations are still widely used in quantitative maturation simulations.
Their potential to adequately model the evolution of vitrinite reflectance has in
fact been demonstrated in many cases.
Theoretical considerations confirm, however, that Ttl calculations use a
wrong temperature dependence in connection with the Arrhenius law. Quigley
et al. (1987) observed that Ttl values do not provide an accurate measure of
maturity. For example, the extent of oil generation is significantly under-
estimated with geological heating rates exceeding 1 DC/Mao Considering the
release of phenols from vitrinite under laboratory and natural conditions,
Larter (1989) was the first to arrive at a sound chemical model of vitrinite
reflectance evolution. This and other models (e.g., Sweeney and Burnham
1989) for vitrinite reflectance prediction need to be further tested and im-
proved, however, before the Ttl method can definitely be deemed outdated
(Leischner et al. 1993).
Reflectance of zooclasts and organic particles other than vitrinite were used
in the past to evaluate maturity, especially in pre-Devonian rocks and in other
sedimentary rocks in which no vitrinite is present. Reflectance of liptinite
macerals, for example, sporinite, does not change significantly at early mat-
uration levels corresponding to vitrinite reflectance values below 0.8% (e.g.,
Dormans et al. 1957; Littke 1987). Above this level liptinite reflectance in-
creases more rapidly than vitrinite reflectance. The major disadvantage of
liptinite reflectivity as a maturity parameter is the difference in optical prop-
erties between the major liptinite macerals, i.e., reflectance of resinite, spor-
inite, alginite, cutinite etc. differ greatly from each other (Teichmiiller 1982). In
summary, reflectance of liptinite can serve as reliable maturity indicator only
where the same type of liptinite occurs in a thick stratigraphic section or where
the same type of liptinite occurs in one particular source rock in different
areas.
Bertrand (1990) summarized data on the reflectance of zoo clasts and found
that "chitinozoans and graptolites show similar reflectivity and values slightly
lower than vitrinite, while scolecodents show significantly lower values than
that of vitrinite." Zooclast reflectance is regarded as a valuable maturity in-
dicator in Palaeozoic rocks.
Solid bitumen (compare pyrobitumen, migrabitumen, natural tar; see
Curiale 1986 for chemical information) is a ubiquitous constituent of sedi-
mentary rocks. The potential of its reflectance as a maturity indicator has been
discussed by Jacob (1989). Solid bitumen reflectance was claimed to be an
alternative to vitrinite reflectance, although the data scatter is generally greater
at low levels of maturation « 1% vitrinite reflectance). Reflectance measure-
ments on solid bitumen are more meaningful with mature to overmature
sedimentary rocks where the data display less scatter. These should be inter-
preted with caution, however, since Bertrand (1990) observed discrepancies in
mean reflectance of solid bitumen among various lithologies (sandstone, shale,
and limestone). Also, regression lines between solid bitumen and vitrinite
180 M. Radke et al.
reflectivity were variable among these lithologies. Further studies and more
data are hence needed before solid bitumen reflectance can be regarded as a
reliable maturity parameter.
The observation of progressive color changes of liptinite macerals in
transmitted light with increasing maturation led to the early development of
carbonization measurements on pollen-grains and spores applied in petroleum
exploration (Gutjahr 1966; see Staplin [1977] for historical review). Based on
these observations, the thermal alteration index and level of organic meta-
morphism (Hood et al. 1975) were established as maturity parameters. One
major problem of these parameters is that different liptinites and even different
types of spores differ in their optical properties; accordingly, "each type of
organic matter should have its own scale calibrated to hydrocarbon analysis"
(Staplin 1977). Furthermore, grain thickness greatly affects transmission, and
description of color was until recently a subjective evaluation rather than a
physical measurement. Nevertheless, coloration of palynomorphs and other
particles, such as conodonts (e.g., Noth 1991) and ostracods (e.g., Ainsworth et
al. 1990), was successfully used as a rapid, though rough, estimate of thermal
maturation in many sedimentary rocks. Translucency measurements on one
specific pollen genus (Carya; Eocene-Recent) have been related by Lerche and
McKenna (1991) to thermal history through first-order time-temperature in-
tegrals.
The development of a practicable method providing chemical information
by means of spectroscopy on individual macerals, for example, a microprobe
for organic particles, is still missing (see Blob et al. 1988 for discussion). The
most widely used spectroscopic and microscopic method for characterizing
organic particles in rocks is fluorescence spectroscopy (see Teichmiiller 1986
for historical review; Lin and Davis 1988). Unfortunately, it reveals almost no
chemical information (Pradier et al. 1990). It was noted, however, that most
brightly fluorescing organic particles are hydrogen-rich (oil-prone) immature
liptinites, whereas most weakly fluorescing particles are hydrogen-lean mac-
erals. At increasing maturation stages, fluorescence of liptinites becomes
weaker and is shifted toward longer wavelengths.
From fluorescence spectra a number of parameters were deduced as a
measure of maturity. In this context the most widely used parameters are the
wavelength of maximum fluorescence intensity (Amax), the spectral red/green
quotient (Q), the fluorescence intensity (I), and the alteration of green fluo-
rescence (546 nm) during irradiation. More complex and sophisticated mea-
surements (parameters) were also presented by Hagemann and Hollerbach
(1981), and Michelsen and Khavari Khorasani (1990). Whereas liptinite
fluorescence undisputedly provides a rapid, though rough, estimate of maturity
and can be used in almost all (except overmature) sedimentary sequences, its
applicability as a quantitative maturity parameter is severely restricted by the
great difference in fluorescence properties of different types of liptinite.
Maturation and Petroleum Generation 181
3.4.3
Model for Kerogen Maturation: Evolution of Physical Structure
3.4.4
Changes in Chemical and Carbon Isotope Composition
1.0
°
000
•
°
0.8 ° °•
•
0.6
• •° °
°
• • 0,.,
•
0.4
e
.. ...... .
• •° °
•
• e<t ,
0•
ee~
e ••
0.2 I ••
•
•
o 0.2 0.4 0.6 0.8 1.0
Fig. 3.3. Relationship between the fraction of hydrogen that is aromatic (Ha) and carbon
aromaticity (fa) in coals and coal macerals. Filled circles, whole coals, vitrinites or vitrains;
half-filled circle, vitrinite + inertinite; open circles, inertinites or durains; circles with hor-
izontailine, exinites. (Wilson et al. 1984)
Maturation and Petroleum Generation 183
3.4.5
Pyrolysis Characterization
Pyrolysis has been defined as "a chemical degradation reaction that is induced
by thermal energy alone" (Ericsson and Lattimer 1988). As reviewed by
Horsfield (1984), the technique is well-suited to analyzing macromolecular
sedimentary organic matter fractions, with both simple "bulk-flow" (e.g.,
184 M. Radke et al.
3.5
Bitumen and Petroleum: Geochemical Maturation
3.5.1
Maturation Changes in Bulk Properties and Gross Composition
The API gravity (3.7) is a bulk parameter that allows the maturity of crude
oils to be assessed in the most convenient way. For example, variations in API
gravity of 13°_45° (specific gravity = 0.98-0.80 glml) in an extensive series of
Gulf of Suez oils were attributed to maturities ranging from immature to
mature (Rohrback 1983). The API gravity showed positive correlation with the
percentage of hydrocarbons < CIS and the saturate-to-aromatic ratio, whereas
correlation with sulfur content was negative. A positive correlation of API
gravity with the saturate-to-aromatic ratio has been demonstrated also for a
suite of North Sea oils with API gravities mostly in the range of 25°-45°
(specific gravity = 0.90-0.80 g/ml). In addition, API gravity was shown to be
controlled by the asphaltene content. As a rule of thumb, 15% asphaltene
content in a normal crude oil reduces API gravity by 10° (Cornford et al. 1983).
With siliciclastic rocks, the relative abundance of CIS + hydrocarbons in total
extract generally increases rather regularly from 30% at early thermal evolution
to 60% at the peak of the oil generation curve. Thus, it may be used as a
maturity indicator within this maturity interval, although the large data scatter
allows for only a rough assessment (Foscolos et al. 1976; Powell et al. 1978;
Heroux et al. 1979). Despite the limited precision, a tentative calibration of
relative CIS + hydrocarbon abundance in total dichloromethane extracts against
%Rr proved useful for differentiating oil-impregnated from nonimpregnated
shales (Radke and Welte 1983). This was an important point in the develop-
ment of hydrocarbon-internal maturity parameters because correlation with
%Rr was meaningful only with nonimpregnated samples.
3.5.2
Maturation Changes in Molecular Distributions of Hydrocarbons
.S! 8 ~--------~
I
<0
a:
., 7
<:
to • 6-28-68113'o.'WM
1::
.,c- 6 o 10-35-71113'o.'WM 20 11.tra.ns·2·O!methylcydopenlanej
K.
o II.ds-2-llimOU'lylCy(:loper"ane!
u ::.::
1> 5
>.
.J:; c:til 15
~ 4 iii
c
(5 0
ri' 3 U 10
·u_
II>
o E
.,.~ 2
•
.2
g
<')'
II> -=--.. .::; 5
C C"
,g. .~ UJ
:::.
0.6 0 .8 1.0 1 .2 1.4 1.6 0
0 100 200 300
a Vrtrinite Reflectance, Rr (%) b Temperature (O
el
~ 3~
c .t. .t.
~
~ 2
~
a.
c
o
.0
iii
o
o+I~~
o
Vitrinite Reflectance, Rr (%)
Reaction
A (Reactants) B (Products)
immature =0
k
mature =1.0
H
b Isomerisation of steranes at C-20
immature = 0
mature = 0.55
immature = 0
mature = 0.8
#'-~k #'-~
,,
•
1 ,,
immature =0
mature = 0.6
.~
k
mature = 0.9-1.0
Fig. 3.6a-e. Biological marker reactions in sediments with apparent precursor/product re-
lationships together with starting and end ("equilibrium") values for the corresponding
biological marker compound ratios. (Mackenzie et al. 1985b)
Maturation and Petroleum Generation 193
sufficiently well established for the isomer ratios to be used as thermal mat-
uration indicators (see Mackenzie and Maxwell 1981, Mackenzie et al. 1982a,
Mackenzie 1984 for overviews) and empirical application in petroleum geo-
chemistry was successful in many cases (e.g., Seifert and Moldowan 1981;
Mackenzie et al. 1983; Hong et al. 1986; Li et al. 1987). However, recent hydrous
pyrolysis experiments using oil shale samples showed that there may not be
such a simple precursor/product relationship for sterane isomers, as indicated
in Fig. 3.6b,c (Lewan et al. 1986; Rullkotter and Marzi 1989; Peters et al. 1990;
Marzi and Rullkotter 1992).
As demonstrated schematically by the progress of sterane isomer ratios with
increasing thermal stress in Fig. 3.7a, a reversal to lower values of the 205/
(205 + 20R) sterane isomer ratio of around 0.4 occurs at higher maturity levels
(Rullkotter and Marzi 1989; Marzi and Rullkotter 1992). In contrast to the
expected and theoretically predicted equilibrium value of 0.54 (van Graas et al.
1982), the recursion agrees with low values detected in natural sediment se-
quences (e.g., Mackenzie et al. 1985b; Snowdon et al. 1987). In the past these
a) b) c)
0.6 0.7
0.54 1.0 1.0 0.6 0.61
0.5
0.8 0.5
0.4
0.6 0.4
O.S
0.3
0.2 0.4
0.2
0.1 0.2
0.1
0.0 0.0 0.0
Hydrous Pyrolysis
....... Increasing Thermal Stress
Fig. 3.7a-c. Predicted (above) and observed (hydrous pyrolysis; below) extent of biological
marker reactions with the x-axis showing the thermal stress in arbitrary units. a Isomerization
of C29 steranes at C-20. b Transformation of C-ring mono aromatic into ABC ring triaromatic
steroid hydrocarbons. c Isomerization of 17!X-homohopanes at C-22. (Marzi and Rullkotter
1992)
194 M. Radke et al.
-10 r---------------------------------------------,
Ea = 169.0 kl/mol
- 15
A = 4.86xl0 8 s-1
Correlation Coefficient = 0.99
- 20
,......,
.:r I North Sea and Pannonian Basin I
::s - 25 I Hydrous Pyrolysis I
- 30
1
- 35
o
-40 ~----_.----_.------r_----,_----_.----_,r_~~
(l/T)xlOOO
Fig. 3.8. Arrhenius diagram for determination of kinetic data of sterane isomerization based
on hydrous pyrolysis experiments and selected natural samples from the North Sea and the
Pannonian Basin (Mackenzie and McKenzie 1983). (Marzi and Rullkiitter 1992)
Maturation and Petroleum Generation 195
Mackenzie and McKenzie (1983), a sensitivity analysis showed that both sets of
data react in a similar way when applied to the geothermal histories of sedi-
mentary basins (Marzi et a1. 1990). This is in contrast to kinetic data for
apparent sterane isomerization determined by Suzuki (1984) and Sajgo and
Lefler (1986) which do not seem to be geologically meaningful (Marzi et a1.
1990). Also, the kinetic data of Abbott et al. (1990) based on the more so-
phisticated view of new formation and destruction of steranes cannot be ap-
plied to geological systems but seem to be valid only for the laboratory
experiments performed (Marzi 1992; Abbott et a1. 1992). Despite the fact that
sterane isomerization at C-20 is apparently not a geochemical reaction with a
straightforward precursor/product relationship, empirical application of the
(pseudo) kinetic data for sterane isomerization has led to novel conclusions
with respect to the geothermal histories of sedimentary basins (e.g., Mackenzie
and McKenzie 1983; Marzi and Rullkotter 1992; Rullkotter et a1. 1992). In the
case of the Michigan Basin (Fig. 3.9) both measured and calculated sterane
isomerization values showed that there has been higher geothermal heat flow
in the past than assumed from geophysical modeling (Marzi and Rullkotter
1992).
Sterane isomer ratios obviously cannot be applied as maturation indicators
in carbonates, siliceous or phosphatic sediments and evaporites, or crude oils
0 ,0 iUx'-dr------,t r _ - -- -- -- -- - - - - - - - --r-----rO,5
E. Devonian
-0 ,5 '-./ 0.5
-, .0 0.4 Cj)
o
•
E C 3
.>t:
;; -' .5 Coldwater Shale ~ <D
0.3 ijl'
a.
Q)
Q)
g
o -2,0 P 0.2 :I
Fig. 3.9. Late Palaeozoic subsidence of the center of the Michigan Basin (solid lines) and
calculated evolution of sterane isomerization (dotted lines) based on a modified geothermal
scenario (higher heat flow and deeper subsidence during the Carboniferous) relative to that
based on geothermal modeling. Ranges of measurements (bars) on natural samples are shown
for comparison. D, Early Devonian; A, Antrim Shale; C, Coldwater Shale; P, Pennsylvanian
coal. In contrast to that put forward by Nunn et al. (1984), oil generation in the Michigan
Basin occurred early in Devonian and older strata and was even possible in late Devonian
sediments. (Marzi and Rullk6tter 1992)
196 M. Radke et al.
derived from these sources. As an example, oils and asphalts from the Dead Sea
area were found to have uniform sterane isomer ratios despite large differences
in thermal maturation as evident from other maturity parameters such as
steroid aromatization (Rullkotter et al. 1985). Ten Haven et al. (1986) found
that specific steroid precursor molecules with a double bond at C-7, bio-
synthesized by organisms thriving in (hypersaline) environments where de-
position of carbonates and evaporites occurs, are responsible for early
isomerization at C-14, C-17, and C-20 in the steroid molecules. A facies de-
pendence of sterane isomerization at C-14 and C-17 in the early catagenesis
stage was also found in Lower Toarcian carbonate-rich shales and marls and
adjacent mudstones from the Hils syncline in northern Germany (Fig. 3.10;
Rullkotter and Marzi 1988). In the same sample series, sterane isomerization at
C-20 showed no facies dependence (Fig. 3.10).
Ubiquitous hopanes of bacterial origin in sediments and crude oils are
another class of biological marker hydrocarbons that undergo systematic
changes as a function of thermal stress in sediments. The hopane isomer ratios
in general are more dependent on the source of organic matter than sterane
isomer ratios, and several of the apparent hopane isomerization reactions
(Fig. 3.6d,e) are also complete before oil generation really starts (Seifert and
Moldowan 1980). Moretanes (17~,21Cl-hopanes) are common constituents of
several land plant species and thus may be directly incorporated into sediment.
This complicates their use as maturity indicators in the case where the or-
ganofacies of the sample series investigated varies. For a series of coals, ten
Haven et al. (1989) have studied moretane/17Cl-hopane transformations in
some detail. A slight facies dependence of the 17Cl-hopane/moretane ratio is
obvious for the Liassic sample series from northern Germany.
Isomerization in the side-chain of extended 17Cl-hopanes (C 31 -C3S ;
Fig. 3.6d) is complete at the onset of catagenesis (Mackenzie et al. 1980;
Mackenzie 1984). In hydrous pyrolysis experiments on Lower Toarcian shales
from northern Germany the 22S/(22S + 22R) ratios of extended hopanes unlike
the steroid hydrocarbons do not show a reversal in their trend at high thermal
stress (Fig. 3.7c; Marzi and Rullkotter 1992). In a similar experiment Peters et
al. (1990) found a reversal in the trend of 22S/(22S + 22R) ratios of 17Cl-
homohopanes at high temperatures (> 340 DC) for the phosphatic member of
the Monterey Formation but not for the siliceous member. They could not
exclude problems in determining this ratio precisely with the low amounts of
hopanes remaining at these high temperatures. There is also no facies de-
pendence of this ratio in the core sequence of Lower Toarcian and adjacent
rocks from northern Germany (Fig. 3.10).
In contrast to this, the ratio of 22,29,30-trinor-neohopane (Ts) to 22,29,30-
trinor-17Cl-hopane (Tm) shows a strong facies dependence (Fig. 3.10). This
hopane parameter is known to be both source and maturity dependent (Seifert
and Moldowan 1978), with the neohopane component being the more stable
isomer. Again, the use of this parameter is limited to sequences with uniform
organofacies characteristics.
Steroid hydrocarbons with ring A or B aromatized are formed during early
diagenesis (Hussler et al. 1981; Hussler and Albrecht 1983) but are relatively
0 0
2::::
6.6. 6. 6. 6. e:,
10 6. 6. e:, e:, 8-...
6. 6. 6. e:, 6. ~ 10 ~ ~
I-< o·
4) ::l
6. 6. 6. e:, b() P>
20 6. b e:, 6.e:, e:, b() ::l
0-
e:,
t20 0
6. b 6. e:,
Cl (t>
q
'"
0
30 6. 6. e:, 6. 6 rn
..-... 6. 6. e:, e:, 6 ~
S
'-"
6. e:, e:, e:, e:,
[30 3
CJ
(t>
b e:, 6A ::l
40 (t>
-5p... 40 0 ....
P>
0 c ::to
~ 00 >J' 0
Cl
--- ::l
~o 0 ~
50
0 00 ~
, ~
gO c90
0 1[50 +
'-""
w
60 00
% 60
C§ 19<9 ~
~ ~
70 70 co
~
80 I I I 180 ~
0.40 0.50 0.40 0.50 0.60 0.70 0.80 0.45 0.55 0.66 0.10 0.20 0.30 0.40 0.50 0.60 0.70 0.80 0.90 1.00
S<erane Isomerioation Srerane Isomerisation Hopane Isomerioation C !7 -Hopane Ratio Hopane / Moretane Ratio
2OS/(20S+2OR) fjfj/( fjfj+ <X<X) 22S/(22S+22R) "Th/(n+Tm) hop/(hop+ mor)
Fig. 3.10. Biological marker compound ratios as a function of depth in borehole samples of Lower Toarcian carbonate-rich shales and
marls and adjacent mudstones from the Hils syncline, northern Germany. Sterane isomerization at C-14 and C-17 W~/(~~+crcr)], C27
hopane ratios and 17cr-hopane/moretane ratios show distinct facies dependence, whereas sterane isomerization at C-20 and iso-
merization of 17a-homohopanes at C-22 do not (Reprinted from Rullkotter J, Marzi R., Natural and artificial maturation of biological .....
markers in a Toarcian shale from northern Germany. In: Mattavelli L, Novelli L (eds) Advances in organic geochemistry 1987. '-J
'"
Pergamon Press, Oxford, 1988, pp 639-645, with kind permission from Elsevier Science Ltd, The Boulevard, Langford Lane, Kidlington
OX5 1GB, UK)
198 M. Radke et al.
unstable and disappear again when diagenesis proceeds further (Rullk6tter and
Welte 1983). They are followed by C-ring monoaromatic steroid hydrocarbons
(Riolo and Albrecht 1985; Riolo et al. 1985; Moldowan and Fago 1986) at a later
diagenetic stage. They persist well into the catagenesis zone where they are
gradually transformed into ABC ring triaromatic steroid hydrocarbons
(Mackenzie et al. 1981; Ludwig et al. 1981). This apparent transformation
(Fig. 3.6a) was introduced as a maturation indicator based on a tri-/(tri- +
mono-) aromatic steroid hydrocarbon ratio by Mackenzie et al. (1981). It was
later modified by Moldowan and Fago (1986) due to the identification of new
series of (rearranged) monoaromatic steroid hydrocarbons and enhanced gas
chromatographic resolution.
The tri-/(tri- + mono-)aromatic steroid hydrocarbon ratio, as the sterane
isomer ratio, shows a reversal in its trend with increasing thermal stress both
in hydrous pyrolysis experiments (Fig. 3.7b; Rullk6tter and Marzi 1989; Peters
et al. 1990) and in natural sample series (Mackenzie et al. 1985b). This indicates
that at elevated temperatures the preferential thermal destruction of the more
labile triaromatic species becomes more important than the conversion of
mono- into triaromatic steroid hydrocarbons. It should be noted, however, that
at this level the absolute concentration of aromatic steroid hydrocarbons has
decreased by about three orders of magnitude compared to the early cata-
genesis stage (Rullk6tter et al. 1984; Marzi and Rullk6tter 1992).
The aromatic steroid hydrocarbon maturation parameter seems to be more
widely applicable than the sterane isomer ratios, i.e., steroid aromatization is
less dependent on organic facies but reacts virtually only to thermal stress. This
has been demonstrated in the maturity assessment of carbonate-derived as-
phalts and crude oils from the Dead Sea area, Israel (Rullk6tter et al. 1985),
from a series of 50 crude oils from various sources (Riolo et al. 1986), and a
series of sulfur-lean and sulfur-rich crude oils from the Monterey Formation in
California (Rullk6tter and Orr 1989). In the latter case maturity assessment
using sterane isomer ratios failed for sulfur-rich oils but was applicable to
sulfur-lean Californian oils, whereas the steroid aromatization parameter was
able to discriminate within the entire set of oils according to maturity differ-
ences (Fig. 3.11).
Besides mono- and triaromatic steroid hydrocarbons with intact carbon
skeletons (mainly CS-C lO side-chains) there are the corresponding lower
pseudohomologs with short side-chains (C r C3 ) in sediments and crude oils.
Although this has never been proven, the idea is that the short side-chain
species derive from their higher pseudohomologs by thermal cleavage of the
side-chain (Mackenzie et al. 1981). Empirically the ratio of short to long side-
chain aromatic steroids was found to be a maturation parameter particularly in
the higher maturity range (Seifert and Moldowan 1978; Mackenzie et al. 1981,
1985b; Shi et al. 1982; Riolo et al. 1986). Recently, Lichtfouse et al. (1990) found
a new series of 3- and 4-methyl triaromatic steroids (C 21 -C23 ) in marine shales
from the Paris Basin. The concentration of 3-methyl triaromatic steroids sys-
tematically increased with maturity relative to the concentration of the cor-
responding 4-methyl isomers. Based on the assumption that this is due to a
thermally induced methyl group shift from C-4 to C-3 in ring A of the
Maturation and Petroleum Generation 199
+
-~.~--"--- .., - - " - - - - - - , - - - -
0.5
i:2'
• •
0
CN
+ •
. •
0.4
•
r:/l
.. • • •
0
~ •
'-..
r:/l
0
CN
• • ••
0.3
i::
• •
0
'ao:l
.>::'"
•
v
••
-S
0.2
S
0 •
'"v
0.1
~
r:/l
0 T [ -----r-------,----.---r--r----. "
0 0.2 0.4 0.6 0.8 1.0
Steroid Aromatisation: tri-/ (tri- + monoaromatic)
Fig. 3.11. Cross plot of sterane isomerization and steroid aromatization for crude oils from the
Monterey Formation. Sulfur-rich oils (circles) exhibit uniform sterane isomerization values
whereas sulfur-lean oils (squares) can be differentiated by both parameters. (Rullkiitter and
Orr 1989)
o
0.7
n
~
.......
l:R
.........
0 0 1''''0 r=0.96
~ 0.9 .~ (n= 16) ~
o ""0.3> '0
,§
~
a
(,,) o 0 ;:>
E(,,)
<I)
1.1
o
o
o~
Ci:l
~,.
~ 1.3
......................
.................. 0 ............................ i
.....
<I) ·······
'S o
'E 1.5 o
;> o
1.7 o
o
1.9
Fig. 3.12. Relationship between MPI 1 and mean random vitrinite reflectance for rock samples
from a borehole in the Elmworth area, western Canada. (Radke et al. 1982a)
Maturation and Petroleum Generation 201
marginally mature stages was indicated for Miocene coals with OAO-O.64%Rr of
the Mahakam Delta, Indonesia by a linear increase in the MPI 1 with depth
(Garrigues et al. 1988a). Regression analysis of MPI 1 data for Australian rock
samples of Carboniferous, Permian, Jurassic, and Tertiary ages containing
terrestrial organic matter suggested that calibration against %R r generally may
be extended to 0.5%Rr (Boreham et al. 1988). Discrepancies among MPI 1 and
%R r or Tmax of certain oil-prone source rocks, however, left the significance of
maturity parameters below 0.7%R r based on phenanthrenes open to doubt
(Radke et al. 1986; Radke 1987; Cassani et al. 1988; Lu and Kaplan 1989).
In Tertiary and Jurassic rocks of the Upper Rhine Graben erratic MPI 1
variations at 0.30-0.67%Rr were suspected to arise from migrated oil (Radke
and Welte 1983). In order to improve understanding of these unexpected aro-
matic hydrocarbon distributions in sediments of apparently low maturity, a
wider range of extractable aromatic hydrocarbons were investigated in four
boreholes of the Upper Rhine Graben, three of which had been studied for
maturity indicators based on methyl- and dimethylphenanthrenes (Radke and
Welte 1983; Radke et al. 1991). Alkylated phenanthrenes showed a regular
thermal evolution with depth only for the borehole Kork 1 (Fig. 3.13), as in-
dicated by an increase in MPR and MPI 1. In organic-matter-Iean immature
sediments of the other boreholes alkylated compounds generally were out-
ranked by nonalkylated (parent) compounds. Phenanthrene, fluoranthene, and
pyrene along with minor amounts of monomethyl- and dimethylphenanthrenes
presumably were associated with organic matter that had been severely altered
in high-temperature and/or oxidative conditions before it was finally in-
corporated into the sediments. During catagenesis these PAHs retained a pyro-
lyticlike distribution until, depending on type and amount of unaltered
autochthonous organic matter in the same samples, alkylated aromatic hydro-
carbons released from kerogen eventually became more abundant. The MPI 1
was a useful maturity indicator only where those latter hydrocarbons prevailed.
In some of the organic-matter-Iean samples where an enhanced abundance of
methylated relative to parent compounds was attributed to migrated oil, the
MPI 1 was higher than expected and believed to reflect the maturity of the oil.
The potential of the MPI 1 for assessing oil maturities has been tested with
more than 200 crude oils of various origins (Radke 1987, 1988). A preliminary
classification into immature, mature, postmature, and overmature categories
was refined when influences of the organic facies were taken into account. Four
modes of the Rc frequency distribution were tentatively attributed to types I,
VII, IlIIll, and Ill/II of the source kerogens (Fig. 3.14), because the modes at
0.75%, 0.82%, and O.92%Rc corresponded to maxima of the hydrocarbon
generation curves generally assumed at the respective %Rr values. The first
mode at 0.65%Rc> however, was lower than expected for oils derived from type
I kerogen-bearing strata, which likely were the source beds of oils from the
Songliao Basin. This discrepancy may be due to the fact that calibration of MPI
1 against %Rr was based on humic coals and type III kerogen-bearing rocks. As
the impact of organic facies on the MPI 1 is reduced with increasing maturity,
Rc values are particularly useful for assessing the maturity of postmature oils
and condensates, which generally is outside the dynamic range of biomarker
202 M. Radke et al.
MPR MPII
0 0.5 1.0 1.5 2.0 2.5 0 0.4 0.8 1.2
200
o Weitenung 1
'" Soe1lingen 1
400 • Kork 1
J
o Kork2
600 °0
800 q/D
\'0
1000
,-.....
6
~!
'-' 1200 /
.s0.. d
/
II)
1400
0 \
6
1600
•\/¢Y
1800
2000
2200
2400
Fig. 3.13. Variation in MPR and MPI 1 with depth for rock samples from four boreholes in the
Upper Rhine Graben. (Radke et al. 1991)
parameters. The MPI 1 parameter has been successfully used in numerous oil
studies that are mostly unavailable from the open literature. Published appli-
cations include maturity assessment of l30 crude oils representing 107 oil
pools in the Cooper and Eromanga basins of Australia (Tupper and Burckhardt
1990), 60 crude oils from different regions of the former Soviet Union (Ivanov
and Golovko 1992), and 60 crude oils from three Java Sea (sub-}basins (Radke
et al. 1994).
Maturity parameters based on alkylated biphenyls rely on an abundance
decrease with maturity of 2-methylbiphenyl or 2,3-dimethylbiphenyl (2,3-
DMBP). Lower stability of isomers with a methyl group in artha (2) position as
compared to those with methyl groups in para (4) or meta (3,5) positions has
Maturation and Petroleum Generation 203
10
II/III
""'"'
tf2. I/II
~
c:Q) 5
6-
Q)
1II/lI
Fig. 3.14. Frequency distribution of Rc for crude oils of different origins. (Radke 1987)
3.5.3
Maturation Changes in Molecular Distributions of Heterocompounds
The effect of maturation on sulfur aromatics has been demonstrated for Middle
East crude oils where the abundance relative to alkylbenzenes of alkylben-
zo[blthiophenes decreased as maturity increased (Joly et al. 1974). The ben-
zothiophene-to-dibenzothiophene ratio introduced by Ho et al. (l974) relies on
the lower stability of alkylbenzo[blthiophenes as compared to alkyldi-
204 M. Radke et al.
100r---------:.,--.,----,
eJuplter#1
• Madeleine #1
150
Heating rates
(OCxMa-1 )
50
Fig. 3.15. Curves showing theoretical progress of reaction with increase in temperature based
on laboratory-determined kinetic parameters for the cyciization of 2,3-dimethylbiphenyl and
the heating rates of the sediments in boreholes Jupiter #1 and Madeleine #1. Solid circles and
squares, 3,S-DMBP/2,3-DMBP values measured for sediment samples. (Reprinted from
Alexander et aI., 2,3-Dimethylbiphenyl: Kinetics of its cyciisation reaction and effects of
maturation upon its relative concentration in sediments. In: Mattavelli L, Novelli L (eds)
Advances in organic geochemistry 1987. Pergamon Press, Oxford, 1988, pp 833-837, with kind
permission from Elsevier Science Ltd, The Boulevard, Langford Lane, Kidlington OXS 1GB,
UK)
1.1.-----------------------------------------~--~
.-..
0~
'-"
~ 0.9
0::
<Ii
u
c 0.8
til
"0
Q) 0
;;::::
Q) 0.7 "0
0:: o WEA. TYPE 1111
Q) o POS. TYPE 1111
~ " KIM. TYPE II
C 0.6 o CRE. TYPE II
.....
'i:
•
0
• • CRE, TYPE III
:> •
• L+D, TYPE III
0.5 •
••
0.4
0 2 3 4 5 6 7 8 9
470
460
450
.-..
.. .
·.
0
()
0
410
0 2 3 4 5 6 7 8 9
Fig. 3.16. Relationship between MDR and mean random vitrinite reflectance (a) and Tmax (b)
for rock samples of different origins. (Radke 1988)
206 M. Radke et al.
Jensen (1966) who observed that the ratio of DPEP to ETIO porphyrins was
lower in the shale oil derived from retorting of Green River Shale than in the
starting material. This change likely was due to thermal destruction of DPEP,
rather than to a conversion of DPEP to ETIO porphyrins by opening of the
isocyclic five-membered ring, as indicated by heating experiments on artificial
vanadyl DPEP and vanadyl ETIO porphyrin mixtures (Burkova et al. 1980).
The ETIO porphyrin survived a 10-h heat treatment at 220°C, whereas most of
the DPEP was degraded.
From the variation with depth in carbon-normalized yields of both porphyrin
types in El Lajjun Shale (Jordan) it was deduced that changes in the DPEP to
ETIO porphyrin ratio not only were due to the higher thermal stability of the
ETIO porphyrins but also to generation of those compounds from kerogen
(Barwise and Roberts 1984). The percentage of deoxophylloery-
throetioporphyrins (DPEP) in total porphyrins from Permian Marl Slate (Dur-
ham, England) sediments exhibited high sensitivity to maturity at 0.3-0.7%Rr.
Thus, it is an attractive alternative to %R r for maturity assessment of samples
with high porphyrin contents, such as algal-rich sediments, where %R r generally
is difficult to measure (Barwise and Park 1983). A related vanadyl porphyrin
maturity parameter (3.10) has been introduced by Sundararaman et al. (1988):
PMP = Cz8 E/(C Z8 E + C32D) (3.10)
where Cz8 E is ETIO porphyrin with 28 carbon atoms, and C32D is DPEP
porphyrin with 32 carbon atoms
Using pyrolysis experiments those authors were able to scrutinize earlier
models for porphyrin conversions during catagenesis. According to their results,
the thermal evolution of vanadylporphyrin distributions is controlled by the
generation of ETIO porphyrins that would increasingly dilute preexisting DPEP
porphyrins. The potential of the PMP parameter for assessing the maturity of
marine source rocks and crude oils has been demonstrated with hydrous pyr-
olysis experiments and several field examples (Sundararaman and Raedeke 1993).
The effect (2) arises from alkylation-dealkylation processes and/or forma-
tion of polyalkyl porphyrins from bacteriochlorophylls (Chicarelli et al. 1987;
Ocampo et al. 1987 and references therein). Variations in the extent of alkyl-
ation beyond C3Z are measured by an alkylation index (Baker et al. 1967; Baker
and Palmer 1978). When plotted against the percentage of DPEP, the alkylation
index reaches a maximum greater than 1.0 around 60% DPEP (Baker and
Louda 1986). The ETIO porphyrin ratios, Cz8 E'/C Z7 E' and Cz9 E'/C 28 E', proved
useful in maturity assessment of postmature marine crude oils and rock ex-
tracts (Gallango and Cassani 1992).
3.5.4
Maturation Changes in Carbon Isotope Composition
reflects total swamping by generated oil of initial oil. This interpretation agrees
with that of Schoell et al. (1983) and Schoell (1984) who attributed variations in
the isotopic composition of organic extracts from sedimentary rocks of the
Mahakam Delta, Indonesia, to mixing of isotopically light initial soluble or-
ganic matter with isotopically heavier generated oil.
3.5.5
Thermochemistry, Kinetics, and Mechanisms of Molecular Transformations
The methyl group at the ortho (2) position of biphenyl, although thermally
relatively unstable, is not shifted because it enters into a cyclization reaction to
give fluorene at elevated temperatures. In a kinetic study on the conversion of
2,3-dimethylbiphenyl, 1-methylfluorene was in fact the only significant reaction
product (Alexander et al. 1988). For determination of the kinetic parameters,
solutions of the substrate in Dexsil were heated without a catalyst in sealed
ampoules at five temperatures between 460 and 500°C for appropriate times in
the range 40 min-21 h. As expected, the reaction was first order [activation
energy: 181 kJ mol- I(43 kcal mol-I), frequency factor: 8.2X10 7 s- l j. With
naturally matured sediments, however, the ratio of 2,3-dimethylbiphenyl to 1-
methylfluorene did not change with maturity in a systematic way. Because 1-
methylfluorene obviously originated also from other sources, it was unsuitable
as a reference when monitoring 2,3-dimethylbiphenyl conversion in sediments.
Instead, the 3,5-dimethylbiphenyl finally chosen for this purpose proved inert
under conditions that resulted in complete conversion of 2,3-dimethylbiphenyl
to 1-methylfluorene. A more detailed investigation of ortho-methylbiphenyls
included mono-, di-, and trimethyl derivatives that were partially deuterated in
the benzylic position. It showed that the cyclization reaction involved a ther-
mally induced homolytic cleavage of the benzylic C-H bond as the rate de-
termining step (Kagi et al. 1990). Regarding application to maturity assessment
of sedimentary rocks, it is important to note that the reaction is uncatalyzed.
Lithological variations do not affect the reaction rates in this instance.
Of the semiempirical quantum mechanical methods for calculating ther-
mochemical data of molecules as a function of molecular geometry, molecular
mechanics (MM; see Kao and Allinger 1977) and a method based on the zero-
differential overlap approximation (complete neglect of differential overlap or
CNDO; see Pople and Beveridge 1970; Murrel and Harget 1972) have been
applied in organic geochemistry. Energies of molecules at their ground states
were obtained by the MM method, while the total energy as a function of H-
Co .. H distances was assessed by CNDO calculations. An improved version
(MM2, CNDO-2) that differed from the original method by modified param-
eterization was employed in each case. Accordingly, van Graas et al. (1982)
used the MM2 method for calculating heats of formation (gaseous standard
state) of 13 cholestane isomers and predicted the extent to which isomerization
reactions can proceed during maturation. Thermodynamic stabilities of var-
ious alkylated, dealkylated, and rearranged 17a- and 17~-hopane isomers were
likewise assessed by Kolaczkowska et al. (1990). They observed that calculated
equilibrium ratios of certain isomers generally agreed with those found in
thermally mature crude oil samples. To calculate relative differences in free
energy of 32 cholestene isomers increments of the empirical MM2 force field
had to be adjusted for Sp2 hybridized carbon atoms. From these results it
follows that double bond isomerization via secondary carbocations is unlikely
(de Leeuw et al. 1989).
The MM2 method has also been used to verify the greater stability of ~-type
when compared to a-type methylphenanthrenes, thus to substantiate the
chemical basis of the MPI 1 (Garrigues et al. 1990). Because for 2-MP and 3-MP
calculated enthalpies of formation of 41.9 kcal mol- I are less positive than for
Maturation and Petroleum Generation 209
I-MP and 9-MP (43.8 kcal mot l ) a negative heat of isomerization of -1.9 kcal
mot l (gaseous standard state) is inferred. Correspondingly, based on pub-
lished heats of combustion, a negative heat of isomerization of -5.8 kcal mot l
was assessed for 9,10-DMP to yield 2,7-DMP (Radke et al. 1982b). As long as
entropies of formation of the compounds of interest are unknown, free en-
ergies of formation (L1G°f,T)' cannot be determined. Predicting thermodynamic
equilibrium distributions is therefore critical with methylated phenanthrenes.
This is in contrast to dimethyl-, trimethyl- and tetramethylnaphthalenes where
thermodynamic equilibrium distributions were based on L1G°f,T (I) of each
isomer (3.11) using an increment method (Garrigues et al. 1988b) or the MM3
force field (van Duin et al. 1993). However, the results should be considered
with caution also in this instance. It must be kept in mind that the thermo-
chemical data refer to the gaseous standard state, which will never occur in a
geological system:
N,
AGf,T(1) =RT In[L exp(AGhJ/RT] (3.11)
i=l
-0.16 0.16
Fig. 3.17. Structural changes of a simplified "epimerization siton" by the "assisted vibrational
displacement mechanism" and total energy function for this reaction. (Costa Neto 1988)
3.5.6
Relationships Among Various Maturity Indicators
i I{I{ _ _
- - - CeItIon tUnbIr
- - - - - DPEP.£I1O
; II{c-------o--=~--:-:-:..-:~
'E'l
l 0 - - - - - ~ 2088t1r1n11
I ~--0
o
U
i
HopInII
228, 17.H HopInII
8... Ii IIIIIO-PItIIIIII
VIb1nIte Reftectance
~
"Co
----oqo----q--~---q-
~ 9'" P'
if~I§0 - - - -
Fig. 3.18. Ranges of individual molecular measurements of thermal maturation relative to a
downhole hydrocarbon generation curve and a vitrinite reflectance scale. (Mackenzie and
Maxwell 1981)
0.------------------------,
~ 10
•
:!
; 20
CiS
.....
~50 0;==
· ~=~Basln
100 80 60 40 20 0
Tri-I (Tri- + Mono-) aromatic Steroid Hydrocarbons (0/0)
Fig. 3.19. Comparison of the variation of the extent of steroid aromatization relative to the
extent of sterane isomerization at C-20 for an assumed quiescent geothermal regime (North
Sea) and an area of high heat flow (Pannonian Basin). (Mackenzie 1984)
Maturation and Petroleum Generation 213
0.5
0.4
~
.9 0.3
drJ'l
·c
Q)
S
0
0.2
.....rJ'l
0.1 * 1.0'CIMa
-B- 10 'CIMa
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
Aromatisation
Fig. 3.20. Simulated progress of sterane isomerization and steroid aromatization using kinetic
data determined by a combination of hydrous pyrolysis and natural samples and assuming
heating rates of 1 and 10°C Ma -I. In contrast to earlier kinetic assessment of these two
geochemical reactions the difference of temperature effect is only minor. (Marzi and Rull-
katter 1992)
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4.1
Introduction
lrnstitut fiir Erda! und Organische Geochemie (ICG-4), Forschungszentrum Julich GmbH,
52425 Julich, Germany
4.2
Concepts of Chemical Kinetics
4.2.1
Rate Laws and Order of Reactions
The increase or decrease per unit time of the concentration of the molecular
species participating in a given reaction is termed the rate of the reaction or
conversion rate. In a well-defined chemical reaction performed under con-
trolled conditions the conversion rate can be expressed by the rate of change of
concentration of each compound participating in the reaction. The rate of
decrease in the educt concentrations is related, through the stoichiometric
coefficients, to the rate of increase in product concentrations.
For the generalized stoichiometric Eq. (4.1) the conversion rate is given by:
d(A) d(B) 1 d(C) 1 d(D)
(4.4)
nA dt nB dt ne dt nD dt
Here the parentheses denote the concentrations of the individual components.
Most theories of chemical kinetics have evolved from the idea of collisions
of molecules either in the gas phase or in solutions resulting in a chemical
reaction. Evidently, the rate of a reaction:
A + B----+C (4.5)
236 H.J. Schenk et al.
4.2.2
Temperature Dependence of Reaction Rates
perature, the rate coefficient of the "rule of thumb" Eq. (4.12) increases in-
finitely with temperature. The logarithm of k(T) in Eq. (4.12b) is a linear
function of temperature (T) whereas in Eq. (14b) a hyperbolic relationship is
obtained.
A more sophisticated theory of chemical kinetics, the transition state theory
(TST) was developed by Eyring (1935a,b) on the basis of statistical thermo-
dynamics. The TST predicts a similar type of functional relationship for the
temperature dependence of reaction rate as the Arrhenius function but, in
addition, a temperature dependence of the preexponential factor is obtained:
4.2.3
Fundamentals of Non-isothermal Kinetics
M - m = M.exp ( i:
And upon integration (T = To at t = to) one obtains:
Combination of Eqs. (4.19) and (4.20) yields the function for a non-isothermal
generation curve for a first -order reaction:
dm = M~exp(-~ - ~J)
dT r RT r
T (4.21 )
J = / exp ( - :T)dT
To
In a similar way expressions for second- and higher order reactions can be
derived.
240 H.J. Schenk et al.
4.3
Bulk Petroleum Generation
4.3.1
Kinetic Models
is formally very similar to Eq. (4.16) of Section 4.2, with mj being the fraction
of partial bulk petroleum potential Mj which is already transformed into petro-
leum at time t.
The rate constants kj are generally believed to obey the Arrhenius equation
(Eq. 14a, Sect. 4.2) with activation energies Ej expected somewhere between 40
and 80 kcal/mol or 167 and 334 kJ/mol (Ungerer et al. 1986) and pre-
exponential factors Aj that are predicted to be of the order of magnitude of the
frequencies of molecular vibrations (Polanyi and Wigner 1928; Hanbaba and
Jiintgen 1969). Immediate evidence for an Arrhenius-like temperature depen-
dence has been provided partly by heating experiments involving the gen-
eration of CO 2 and H2 0 from solid organic acids (van Heek et al. 1967) and of
gaseous hydrocarbons from coal (Hanbaba et al. 1968; Hanbaba and Jiintgen
1969), and partly by the kinetic interpretation of geological observations such
as the nonlinear increase of extractable bitumen with increasing burial tem-
perature of source rocks (Tissot 1969) or the inverse relationship between age
Kinetics of Petroleum Formation and Cracking 241
Jexp(~~i)dT
T (4.23)
Ji =
o
which closely resembles Eq. (4.21) of Section 4.2 with the current approx-
imation of T0=0.
Equations (4.22) and (4.23) presume a limited number of n parallel reac-
tions or a discrete bulk petroleum potential versus activation energy dis-
tribution. Such discrete models have been reported in many kinetic studies
(Tissot and Espitalie 1975; Ungerer et al. 1986; Ungerer and Pelet 1987;
Burnham et al. 1987, 1988; Espitalie et al. 1988; Schaefer et al. 1990; Issler and
Snowdon 1990; Forbes et al. 1991; Jarvie 1991; Schenk and Horsfield 1993).
These models generally involve the optimization of n+ 1 parameters, namely n
gross hydrocarbon or bulk petroleum potentials Mi associated with the n ac-
tivation energies Ei and one preexponential factor A. The number of param-
eters to be optimized can be reduced by assuming an infinite number of
parallel reactions with a Gaussian distribution of gross hydrocarbon potential
versus activation energy (Pitt 1962; Hanbaba et al. 1968; Campbell et al. 1980;
Braun and Burnham 1987, 1990; Burnham et al. 1988; Mackenzie and Quigley
1988; Burnham and Braun 1990). Discrete models, however, fit better to ex-
perimental hydrocarbon formation rate versus temperature curves, which,
depending on kerogen type and maturity, are more or less asymmetric
(Burnham et al. 1987; Burnham et al. 1988; Ungerer 1990).
4.3.2
Model Calibration Against Programmed-Temperature Open-System Pyrolysis
Although some of the above kinetic models were derived from geochemical
observations in nature (Tissot and Espitalie 1975; Ungerer et al. 1986), most of
them were calibrated against open-system non-isothermal pyrolysis (e.g.,
Rock-Eval) with various temperature programs. Generally, the preexponential
factor A and the gross hydrocarbon potentials Mj associated with the assumed
activation energies Ei are optimized by a least-squares iteration method that
compares measured and calculated bulk petroleum formation rates at a certain
number of temperatures until the corresponding error function (sum of
squared differences) presents a well-defined absolute minimum.
242 H.T. Schenk et al.
.....0\
0\
~ 12
2
t'
c
o
~
E O.B
.E
c
o
£
o
u
o
~ 0.4
:z:
Fig. 4.1. Gross hydrocarbon (bulk petroleum) formation rates (milligram per gram of rock
and per degree) from open-system pyrolysis of a Green River Shale sample as a function of
temperature (DC) at heating rates of 0.1, 0.7, and 5.0 Klmin. (Schenk and Horsfield,
unpublished)
O.1K/min
Toarcian Shale
Fig. 4.2. Gross hydrocarbon (bulk petroleum) formation rates (milligram per gram of rock
and per degree) from open-system pyrolysis of a Toarcian Shale sample as a function of
temperature (DC) at heating rates of 0.1, 0.7, and 5.0 K/min. (Reprinted from Advances in
Organic Geochemistry 1989, Schaefer et aI., Determination of gross kinetic parameters for
petroleum formation from Jurassic source rocks of different maturity levels by means of
laboratory experiments, 1990, pp 115-120, with kind permission from Elsevier Science Ltd,
The Boulevard, Langford Lane, Kidlington OXS 1GB, UK)
244 H.J. Schenk et al.
15
..
01 0.7 5.0 K/min
Indonesian Coal
§
~
E
....o
Fig. 4.3. Gross hydrocarbon (bulk petroleum) formation rates (milligram per gram of coal and
per degree) from open-system pyrolysis of an Indonesian coal sample as a function of tem-
perature (DC) at heating rates of 0.1, 0.7, and 5 K/min. (Horsfield and Schenk, unpublished)
10
O~~~~~~~O+~~~~~~~~~~~~~~~
30 35 40 45 50 55 60 65 70 75 80
Activation energy (kcal/mol)
Fig. 4.4. Gross hydrocarbon potential (milligram per gram of rock) versus activation energy
(kcallmol) as derived from open-system pyrolysis of a Green River Shale sample LMi is the
total potential (milligram per gram of rock) and A is the preexponential factor (per minute).
(Schenk and Horsfield, unpublished)
Kinetics of Petroleum Formation and Cracking 245
0.25
Toarcian Shale
Q.2O
:!
10.15
IM:=88.0 mgJg
~ A =1.1.1Q16 min-1
'0
.~ 0.10
~
0.05
O ~",,~~~~~~~I.~II~.~.hH~.hnrM~rnrl
~
40
I
45 50 55
I
60
I
65
I
70 75
Activation energy (kcallmoll
Fig. 4.5. Fraction of total gross hydrocarbon potential versus activation energy (kcal/mol) as
derived from open-system pyrolysis of a Toarcian Shale sample. LMi is the total potential
(milligram per gram of rock) and A is the preexponential factor (per minute). (Reprinted from
Advances in Organic Geochemistry 1989, Schaefer et al., Determination of gross kinetic
parameters for petroleum formation from Jurassic source rocks of different maturity levels by
means of laboratory experiments, 1990, pp 115-120, with kind permission from Elsevier
Science Ltd, The Boulevard, Langford Lane, Kidlington OX5 1GB, UK)
246 H.T. Schenk et al.
Indonesian Coal
20 [Hi =123.9 mg/g
en
A =5.9.1015 min- 1
.....
.§16
-a
~
c
cu
+-
0 12
0..
C
0
.0
I-
0
u
0
8
I-
"tJ
>.
:I:
O~"rn"TTrnno~~~~~~~~HM~~nn. .,,~
30 35 40 45 50 55 60 65 70 75 80
Activation energy (keall mol)
Fig. 4.6. Gross hydrocarbon potential (milligram per gram of coal) versus activation energy
(kcal!mol) as derived from open-system pyrolysis of an Indonesian Coal sample. LMi is the
total potential (milligram per gram of coal) and A is the preexponential factor (per minute).
(Horsfield and Schenk, unpublished)
25
- 20
~
01
.§
~ 15
i
c
~10
~
~ 5
45 50 55 60 65 70 75
Activation energy (kcal/moll
Fig. 4.7. Gross hydrocarbon potential (milligram per gram of rock) versus activation energy
(kcal/mol) as derived from open-system pyrolysis of Toarcian Shale samples of increasing
maturity. WEN: Rr = 0.48%; HAR: Rr = 0.88%; HAD: Rr = 1.45%. The preexponential factors
are 1.1. 10 16 (WEN), 1.3.10 17 (HAR), and 4.4.10 16 min- I (HAD). (Reprinted from Advances
in Organic Geochemistry 1989, Schaefer et aI., Determination of gross kinetic parameters for
petroleum formation from Jurassic source rocks of different maturity levels by means of
laboratory experiments, 1990, pp 115-120, with kind permission from Elsevier Science Ltd,
The Boulevard, Langford Lane, Kidlington OXS 1GB, UK)
248 H.J. Schenk et al.
factor for all parallel reactions and reflects the increase in this factor by one
order of magnitude in going from the WEN to the HAR stage. Probably these
high energy potentials can still be released during pyrolysis but cannot be
mobilized upon further natural evolution of the kerogen from the mature HAR
to the overmature HAD stage (Witte et al. 1988).
The conclusion that there has been no significant natural generation of oil
and gaseous hydrocarbons during this final maturation step is inferred from
comparative analytical and spectroscopic studies (Witte et al. 1988) which
showed that the total organic carbon content of the shales remained unchanged
in going from the HAR to the HAD stage whereas the aliphatic carbon content
continued to decrease as a consequence of aromatization reactions within the
kerogen. This example illustrates the importance of calibrating laboratory-
based kinetic models against pyrolysis of really immature samples (Tis sot et al.
1987). Similar effects have recently been observed for a series of coals of
increasing maturity (Schenk and Horsfield 1996). In these cases, however, the
increase of potentials at high activation energies was much more pronounced
and pointed to concomitant structural reorganizations and aromatizations
within the coal macromolecule which could be confirmed by infrared spec-
troscopy. Such structural changes within the residual organic matter leading to
an absolute increase in bulk petroleum potentials at higher activation energies
are only detectable if both activation energy distributions and preexponential
factors are optimized individually for each maturation stage; there is no reason
to assume that the model preexponential factors remain unchanged over a
broad maturation sequence.
vi
about 2% which, in the worst case, can add up to an error of (4 + 4) ;::::;! 3% or
12 DC for an extrapolated geological Tmax temperature of 400 K (127 DC). Si-
milar error considerations have been reported by Braun et al. (1991) and
Espitalie et al. (1993).
The formalism of non-isothermal kinetics implies that maximum formation
rates increase whereas Tmax values and curve widths decrease with decreasing
rate of heating (Jiintgen and van Heek 1968). The immediate practical con-
sequences of these well-known relationships are (1) that high geological
heating rates require relatively high paleotemperatures for significant petro-
leum generation to take place, and (2) that these temperatures must be re-
constructed very exactly since main product formation is predicted to occur
within rather narrow temperature limits. The latter fact is a driving force for
even better basin modeling techniques and refinement in the reconstruction of
geological temperature histories (see Chap. 2).
The extrapolation of Fig. 4.8 presumes that laboratory derived kinetic
parameters (preexponential factors and potential vs activation energy dis-
tributions) remain valid under natural heating conditions; the relevance of this
fundamental assumption is discussed in Section 4.5.
2.5..,-------------------...,
1O-12 K/min
~ 1O-11 K/min
~ 2.0
E
.!
1!
.§ 1.5
WEN
l.2 0.1K/min
c:
.8 to
i
~
:z: 0.5
0~--~~--,-~~R¥~~~r__r--~~~~__4
o 100 200 300 400 500 600
Temperature (OC)
Fig. 4.8. Calculated gross hydrocarbon (bulk petroleum) formation rates (milligram per gram
of rock and per degree) as a function of temperature (0e) from open-system pyrolysis of an
immature Toarcian Shale sample (sample WEN, Rr = 0.48%) at a laboratory heatinRrate of
0.1 K/min and two geological heating rates of 10- 12 K/min (0.53 K1106a) and 10- K/min
(5.3 KI10 6 a). (Reprinted from Advances in Organic Geochemistry 1989, Schaefer et ai., De-
termination of gross kinetic parameters for petroleum formation from Jurassic source rocks of
different maturity levels by means of laboratory experiments, 1990, pp 115-120, with kind
permission from Elsevier Science Ltd, The Boulevard, Langford Lane, Kidlington OX5 1GB,
UK)
250 H.J. Schenk et al.
4.3.3
Closed Versus Open -System Configurations
The most common way of gathering kinetic data for gross petroleum genera-
tion is by programmed-temperature open-system pyrolysis. Closed-system
pyrolysis is less convenient to perform because cumulative yields cannot be
measured in a continuous way. Furthermore, most kinetic studies under
confined conditions have been based on isothermal hydrous pyrolysis (Lewan
1985; Barth et al. 1989; Castelli et al. 1990; Hunt et al. 1991). Previous com-
parisons of kinetic parameters derived from Rock-Eval-like and hydrous
pyrolysis revealed significant differences that affect the predicted temperature
ranges of main product formation (Burnham et al. 1987; Burnham et al. 1988).
However, besides the fact that under closed-system conditions a certain
overlap of primary petroleum generation with secondary petroleum cracking
reactions can never be avoided, the observed differences are perhaps linked to
factors other than the open or closed nature of the experiments per se. It is well
known that the Rock-Eval signal is equated to total volatile oil and gas yield,
whereas hydrous pyrolysis kinetics are currently related to the oil fraction that
is expelled from the residual rock and bitumen mixture by rather ill-defined
transport processes which probably interfere with the observed "expelled oil"
formation kinetics. These arguments are further supported by recent oil evo-
lution experiments from a self-purging reactor (Burnham 1991). Whereas the
latter experimental technique can be considered as being intermediate between
rigorously open- and closed-system simulations, the measured temperature
ranges for oil evolution agree essentially with those calculated from open-
system kinetic parameters. Substantial discrepancies are observed, however,
with predictions using the hydrous pyrolysis kinetics reported by Lewan
(1985), partly because single activation energies rather than activation energy
distributions were calculated from the hydrous pyrolysis data (Lewan 1985).
The effectiveness of laboratory-derived kinetic models must finally be
judged according to their ability to accurately predict the timing of bulk petro-
leum generation within a given geothermal history. It is quite obvious that such
predictions should depend exclusively on the type of the organic material on
one hand and on the geological conditions on the other hand. Any strong
dependence on calibration methods would seriously decrease the predictive
value of kinetic models because neither open nor closed experimental con-
figurations can exactly reproduce the degree of confinement of naturally
subsiding source rocks.
In a recent study Schenk and Horsfield (1993) have compared bulk petro-
leum generation from an immature Toarcian Shale sample (sample WEN of
Sect. 4.3.2) under open- and closed-system conditions using directly com-
parable non-isothermal input data in both cases. Open-system pyrolysis was
performed according to the procedure of Schaefer et al. (1990) whereas closed-
system experiments were carried out by use of the microscale sealed vessel
(MSSV) technique of Horsfield et al. (1989). Closed-system pyrolysis of a
kerogen does not allow the continuous registration of hydrocarbon formation
rates as a function of temperature that constitute the most common data base
Kinetics of Petroleum Formation and Cracking 251
~.-----------------------~
-l? 01
(a)
§ 150
~
E
'-
.E 100
E
j
~0.50 0-0 0.1 K /min
f>-t. 0.7 K/ min
0-0 5.0 K/ min
~ 2.8
(b) D.1K/minO.7K/min
~2.4 S.OK/min
E 01
ill E 2.0
o"Q;
..:: d 1.6
OJ '-
0. c: 1.2
~ 0
~ ~ 0.8
E
.E 0.4
O~-r~~-,--.-.-.--.-.-,--.-~
320 360 400 440 480 520
Temperature (oC)
Fig. 4.9. a Cumulative formation of bulk petroleum (milligram per gram of kerogen con-
centrate) during closed-system pyrolysis (microscale sealed vessels) of Toarcian Shale con-
centrates with increasing temperature (Oe) at heating rates of 0.1, 0.7, and 5.0 K/min. Thick
lines, connection between experimental data points; thin lines, spline functions smoothing the
discrete data sets. The concentrates were prepared from sample WEN of Section 4.3.2. b Bulk
petroleum formation rates (milligram per gram of kerogen concentrate and per degree) from
closed-system pyrolysis (microscale sealed vessels) of Toarcian Shale concentrates as a
function of temperature (0C) at heating rates of 0.1, 0.7, and 5.0 K/min. The curves were
calculated as best fit to the first derivatives of the spline functions of a using kinetic param-
eters closely similar to those of Fig. 4.5. (Schenk and Horsfield 1993)
252 H.J. Schenk et al.
10-11 K/min
52 2.0
en
...... Toarcian Shale
en
E
:; 16
.....d
'-
c 10-1 K/min
~
d
12
E
'-
.2
O+--'~T--'~+-~~'--'-'~~~=-~~
o 100 200 300 400 500 600
Temperature (O[)
Fig. 4.10. Calculated gross hydrocarbon (bulk petroleum) formation rates (mg per g of rock
and per degree) as a function of temperature (OC) from open- and closed-system pyrolysis of
an immature Toarcian Shale sample (sample WEN of Sect. 4.3.2) at heating rates of 0.1 K/min
(laboratory) and 10- 11 K/min (nature). For comparison the closed system rates have been
reduced by a factor of 12.7/56.4 according to the increase in organic carbon content from
12.7% (rock) to 56.4% (kerogen concentrate). (Schenk and Horsfield 1993)
Kinetics of Petroleum Formation and Cracking 253
4.4
Generation of Methane and Molecular Nitrogen from Coals
Natural gas accumulations in the Permian Rotliegend and the Triassic Bunt-
sandstein formations of the North German basin exhibit high concentrations of
molecular nitrogen (N 2) ranging from 50% to 90%. Various theories have been
proposed to explain these natural gas "anomalies" (see Krooss et al. 1993,
1995), but the formation mechanism still remains disputed. Natural gas in
northern Germany is sourced by thick strata of Carboniferous coals and dis-
persed organic matter. Coals represent an important reservoir of fixed nitrogen
in the lithosphere, with concentrations ranging between 0.4 and 3 wt%. It is
therefore conceivable that methane and molecular nitrogen in the gas re-
servoirs originated from a common source. Generation potentials of methane
(c. 150 m 3/t organic matter) and nitrogen (7 m 3 /t organic matter) show clearly
that, assuming simultaneous formation and accumulation, N2 contents in
natural gases derived from coals as a common source cannot exceed values of
about 5 vol%. Therefore, if nitrogen-rich natural gas accumulations are derived
from organic matter, their formation requires a mechanism which results in
substantial enrichment of nitrogen over methane. Two hypotheses have been
proposed to explain this enrichment: (1) migration-related fraction-ation
processes resulting in a "chromatographic" separation of methane and nitro-
gen and (2) generation of nitrogen and methane at different stages of sedi-
mentary diagenesis, catagenesis, or metamorphism.
The latter mechanism involves "fractional generation" of methane and ni-
trogen. To test this hypothesis it is necessary to establish the generation ki-
netics of these two gases from coals. The only previous experimental work of
this kind was performed by Klein and Jiintgen (1972). A reevaluation of this
work (Krooss et al. 1993) indicated that phases of preferential generation of
nitrogen may occur during the thermal maturation of coals. On the other hand,
it showed significant shortcomings in the assessment of the kinetic parameters.
Figure 4.11 shows the generation curves for methane and nitrogen from a
low-rank bituminous coal (Rm =0.70%) of the Ruhr area of Germany (Krooss et
al. 1993). These generation curves were obtained with a constant heating rate of
2°C/min from room temperature to 1100 °C (see Lillack 1992, for experi-
mental details). It can be noted that methane and nitrogen generation does not
occur simultaneously during the experiment. Methane formation starts be-
tween 300° and 400°C and in this experiment reaches its maximum rate at
about 500 dc. The generation rate then decreases, and no further methane is
generated above 850 dc. The onset of measurable nitrogen evolution occurs
only above 700°C. The nitrogen generation curve exhibits its first maximum at
780 dc. The most conspicuous feature, however, is the strong increase in the
nitrogen generation rate at extremely high temperatures. This observation
agrees with the results of Klein (1971) who pyrolysed coals of different rank
from the same area. Boudou and Espitalie (1995) performed pyrolysis ex-
periments up to even higher temperatures and found that using a heating rate
of 30 Klmin the second nitrogen peak maximum for semianthracites occurred
around 1200 dc. These experimental results indicate that a significant portion
254 H.J. Schenk et aI.
1.2E-02 1.4E-03
o Methue (meu.) heating rate: 2 Klmin; 20 - 1100 °C
.
1.0E-02 - - Methine (calc.) .. II l.2E-03
• N'ttrosen (men)
1.0E-03
~ S.OE-03
• • • • N'ltrogen (calc.) ~
.
01
0
,,"
~t>O S.OE-04 ~
j
.,.,., . .
~ 6.0E-03
6.0E-04
j ., ....•'-J ,
• ~
~
...
4.0E-03
:::E , ', ' ',~ 4.0E-04
2.0E-03 • 2.0E-04
O.OE+OO O.OE+OO
0 200 400 600 SOO 1000 1200
Temperature [0C]
Fig. 4.11. Formation rates (mg· g-l coal· K- 1 ) of methane and molecular nitrogen as a function
of temperature (0C) during open-system pyrolysis of a humic coal from Northern Germany at
a heating rate of 2 K/min. (Krooss et al. 1993)
of the nitrogen in the coals is very refractory and also under natural conditions
requires excessive temperatures to be liberated.
Based on the experimental generation curves activation energy distributions
for the generation of methane and nitrogen from coal were determined using a
nonlinear least-squares fit procedure described by Schaefer et al. (1990). The
underlying assumptions for this evaluation were that the generation reactions
of both gases can be described by a set of parallel first-order reactions with
Arrhenius type temperature dependence and a single frequency factor.
The calculated generation curves resulting from this evaluation are also
shown in Fig. 4.11. The corresponding kinetic parameters are given in Krooss
et al. (1993). A better constraint on the preexponential factor can be obtained
by performing pyrolysis experiments at different heating rates.
Figure 4.12 shows an application of the experimental kinetic parameters to a
simple scenario of a constant geological heating rate of 4K/106 a. According to
this scenario, formation of natural gas with significant concentrations of mo-
lecular nitrogen occurs only at temperatures in excess of 280 DC. Temperatures
in excess of 300 DC are required to generate gas with N2 as a major component.
Geological studies indicate that these temperature levels may well be reached
by deeply buried Carboniferous strata in the northern part of the North Ger-
man basin. As stated above, cumulative trapping of the generated gas reduces
or even wipes out the compositional effects of fractional gas generation. One
supposition of this model is therefore that the present reservoir gases corre-
spond only to the gas supplied "most recently" on a geological time scale and
Kinetics of Petroleum Formation and Cracking 255
Temperature Cc)
20 60 100 140 180 220 260 300 340 380 420
1-----~----_+------~----+_----~----_+----~~----+_----~--_.~ 1~1e
--Methane
80%
....... Nitrogen
-Nitrogen (Vol.'!.)
20%
o 10 20 30 40 50 60 70 80 90 100
Time (Ma)
Fig. 4.12. Generation rates (m 3It· 106 a) of methane and molecular nitrogen from a humic coal
of northern Germany and nitrogen content (vol%) of methane-nitrogen mixtures vs. time
(10 6 a) and temperature (OC) at a geological heating rate of 4 K/I0 6 a. (Krooss et al. 1993)
therefore represent only a small fraction of the total generated gas. This con-
cept which takes into account the dynamic nature of natural gas accumulations
is supported by gas balance calculations performed by Jurgan et a1. (1983).
According to this study the gas in place in Rotliegend reservoirs of eastern
Lower Saxony corresponds to only 0.1 % of the gas generated within the cor-
responding drainage area. It is therefore reasonable to consider the present day
reservoirs, on a geological time scale, as containers which have been flushed by
large amounts of gas and which represent probes of the gas that has been
supplied most recently.
At present the details of the formation mechanism and evolution of gas
accumulations are far from being understood. One important point to re-
member from the experiments described above is that the products are from
open-system pyrolysis and therefore refer only to primary gases. No account
has been made of the higher molecular weight pyrolysis products, which can
also be considered a potential secondary source of hydrocarbon and non-
hydrocarbon gases. This aspect is discussed in the following section. Newly
established kinetic parameters for methane and nitrogen generation from coals
in combination with basin modeling are expected to provide improved insight
into the sources, composition, and migration pathways of natural gas and the
dynamics and longevity of gas reservoirs on a geological time scale.
256 H.J. Schenk et al.
4.5
The Problems of Predicting Petroleum Generation Rates
and Compositions in Nature
Since the generation of oil and gas from kerogen is controlled by chemical
kinetics, the incorporation of appropriate kinetic models into geothermal
histories, both individually optimized to the source rock of interest, should be a
promising tool for calculating the timing of petroleum formation and reducing
the risk of petroleum exploration. Kerogen, however, is a tremendously com-
plex material, the thermal alteration of which must be anticipated to proceed
through a sequence of competing parallel and consecutive reactions involving
the cleavage of carbon-carbon and carbon-hydrogen bonds, cyclization and
ring-opening reactions, aromatizations, decarboxylations and other elimina-
tions of heteroelements. Gross kinetic modeling of kerogen thermal decom-
position (Sect. 4.3.1) replaces the multitude of actually occurring but unknown
reactions by a finite number of parallel first-order pseudoreactions (reaction
channels), characterized by different initial potentials (partial yields) and ac-
tivation energies. After appropriate calibration (Sects. 4.3.2, 4.3.3) this system
reproduces the overall generation of oil and gas from a source rock during
laboratory pyrolysis and allows the calculation of gross petroleum yields for
any temperature and heating rate. If this artificial scheme remains valid for
geological heating rates, the global amount of petroleum generated from a
source rock up to a defined maturation stage can be rather unambiguously
derived from the subsidence conditions and paleotemperatures according to
Fig. 4.13.
The pyrolytic degradation of an immature kerogen under programmed-
temperature conditions results in the continuous release of hydrocarbons and
related FID detectable species, whose formation rate reaches a maximum
somewhere between 400 and 500 DC, and the concomitant formation of inert
carbonaceous materials. Gross kinetic analysis of product evolution curves,
measured at various feasible heating rates, yields partial hydrocarbon gen-
erating potentials Mi as a function of activation energies Ei generally in the
form of a discrete distribution somewhere between 40 and 80 kcallmol (167-
335 kJ/mol) as well as preexponential factors. The sum of partial potentials is
equal to the area of each evolution curve. Assuming these parameters to be
independent of heating rate, the hydrocarbon formation curves can easily be
calculated for the geological maturation of the same source rock assuming, for
simplicity, that an average geological heating rate (GEOL.dT/dt) can be rea-
sonably derived from the reconstruction of the time-temperature history of the
basin. The drastic decrease in heating rate from about 0.1 K/min (laboratory)
to about 10- 11 K/min (geology) results in a shift of peak generation tempera-
ture down to 100-200 DC and in a strong reduction of curve width. The cal-
culated "geological" dM/dT versus T curve defines the temperature range of
primary bitumen generation under natural heating conditions, and each pa-
leotemperature (GEOL.T E ) is related to a partial curve area (black in Fig. 4.13)
representing the kinetically predicted amount of oil and gas produced from the
source rock up to this maturation stage.
Kinetics of Petroleum Formation and Cracking 257
IMMATURE KEROGEN
:1M
dT G>
m ~
,0 dT
0
p
1-------1'
::r: >
OJ
150 T m o
~ :0
·'lnL
z ~ 400 T
G> o:0
-<
::r:
m
~
MATURE Z
G>
KEROGEN
~~Ul~0l~ DEAD
KEROGEN
TE T
Fig. 4.13. Possible procedure for testing the relevance of extrapolating from laboratory ki-
netics to geological systems.
4.6
The Conversion of Oil to Gas in Petroleum Reservoirs
Crude oils show a progressive increase in gas-oil ratio, API gravity, and hy-
drocarbon content with increasing maturity (Holmquest 1965), and oil oc-
currence ultimately gives way to that of gas and condensates (Landes 1967).
The present day temperature of deepest oil occurrence can lie anywhere be-
tween 90 and 200 DC depending on the area and geological history in question
(see Andreev et al. 1968; Evans and Staplin 1972; Pusey 1973; Evamy et al. 1978;
Zieglar and Spotts 1978; Price 1980; Momper and Williams 1984) and is di-
rectly related to heat flow history, the type and stability of crude oil, dis-
placement phenomena or combinations thereof. Crude oils are commonly
considered to break down via hydrogen transfer reactions to yield gas and
pyrobitumen (Bailey et al. 1974; Connan et al. 1975), the conversion being
assumed to proceed via systems of first-order constituent reactions (Tis sot et
al. 1974; Quigley et al. 1987; Ungerer et al. 1988; Welte et al. 1988; Braun and
Burnham 1990; Behar et al. 1991). Kinetic models of oil degradation are
commonly used, in addition to petroleum generation models (e.g., Ungerer and
Pelet 1987), to help predict the occurrence of oil versus gas in time and space.
260 H.J. Schenk et al.
400
300
200
0.1 K/min
The gas generation curves result from a very large number of individual
chemical reactions, each possessing its own kinetic parameters. While it is not
possible to identify these individual reactions, we can nevertheless identify
some of the processes accompanying gas generation, many of which, such as
increasing paraffinicity, decreasing average boiling point, the high wetness of
generated gases, and the interpreted decrease in asphaltene content, match the
compositional features of naturally matured crude oils (Bailey et al. 1974;
Neumann et al. 1981; Cornford et al. 1983; Tissot and Welte 1984; Claypool and
Mancini 1989). Based on a comparison with these compositional changes, the
2/4-14 petroleum appears to have originated at a stage where a maximum of
15% of the in-place oil had been converted to gas.
The best-fit between measured and calculated gas formation rate curves,
shown in Fig. 4.15, was obtained with the rather narrow gas potential versus
activation energy distribution shown in Fig. 4.16, the principal distribution
being between 66 and 70 kcallmol. The preexponential factor was found to be
6.69· 10 17 min-I. The application of these parameters to geological heating rates
is illustrated in Fig. 4.17. An onset of oil cracking between 160 and 190°C is
indicated for heating rates in the range 0.53 to 5.3 K/10 6 a. According to these
figures, severe oil cracking is not likely to have taken place in the 2/4-14
reservoir as a result of exposure to temperatures around 165°C. These results
are consistent with compositional considerations. Namely, the composition of
the 2/4-14 liquid petroleum bears a resemblance to artificially matured 33/9-14
crude oil at low degrees of conversion «15%).
Numerical modeling using these kinetic parameters and geological input
data specific to the 2/4-14 reservoir predicted that the degree of oil conversion
~ 10
~
Dl
01 07 50 K/min
~8
-a
OJ
L
6
C
0
~
E
L 4
0
"-
til
g,2
....
d
~
0
300 400 500 600
Temperoture (°C )
Fig. 4.15. Total gas formation rates (mg· g-l. K- 1 ) as a function of temperature (OC) for three
heating rates (0.1, 0.7, and 5.0 K/min). Dotted curves, those resulting from differentiation of
the spline functions of Fig. 4.14; solid curves, those calculated from the kinetic parameters of
Fig. 4.16 by the iteration method outlined in Section 4.3.2. (Reprinted from Advances in
Organic Geochemistry 1991, Horsfield et al., An investigation of the in-reservoir conversion of
oil to gas: Compositional and kinetic findings from closed-system programmed-temperature
pyrolysis, 1992, pp 191-204, with kind permission from Elsevier Science Ltd, The Boulevard,
Langford Lane, Kidlington OXS 1GB, UK)
262 H.J. Schenk et al.
160
~140
C71
E120
o
~100
ti
D..
:g 80
C71
:E 6O
.E
040
:;:::
c ~~~~~~~~n~~~~~n~n~~
40 45 50 55 60 65 70 75 80
Activation energy (kcal/mol)
Fig. 4.16. Distribution of initial total gas potentials (milligram per gram) versus activation
energies (kcallmol). The best-fit preexponential factor is A=6.69· 10 17 min-I. (Reprinted from
Advances in Organic Geochemistry 1991, Horsfield et al., An investigation of the in-reservoir
conversion of oil to gas: Compositional and kinetic findings from closed-system programmed-
temperature pyrolysis, 1992, pp 191-204, with kind permission from Elsevier Science Ltd, The
Boulevard, Langford Lane, Kidlington OX5 1GB, UK)
10-12KImin
10-11 K/min
:g4
C71
~
f- 0+-........---1-"""<,--i~.,--....,...=,r--r--.-:::::,...,----l
o 100 200 llO 400 SOO 600
Temperature (0C)
Fig. 4.17. Extrapolation of total gas formation rate (mg· g-I. K- I) versus temperature (0C)
from a laboratory (10- 1 K/min) to typical geological heating rates of 10- 12 _10- 1 K/min (0.53
and 5.3K/l0 6 a). (Reprinted from Advances in Organic Geochemistry 1991, Horsfield et aI.,
An investigation of the in-reservoir conversion of oil to gas: Compositional and kinetic
findings from closed-system programmed-temperature pyrolysis, 1992, pp 191-204, with kind
permission from Elsevier Science Ltd, The Boulevard, Langford Lane, Kidlington OX5 1GB,
UK)
Kinetics of Petroleum Formation and Cracking 263
should be very low at the well location (Andresen et al. 1993). For modeling,
the well had been divided into 38 events extending from the Permian (248 Ma)
to the present day, there being a long period of nondeposition in the Late
Triassic/Early Jurassic but no periods of major erosion. The heat flow history
showed a peak of 1,45 heat flow units (HFU) in the Jurassic, decreasing to a
constant value of 1.15 HFU during the Cretaceous and Tertiary and a rise to
1.30 HFU in the Quaternary. Judging by the results of Schaefer et al. (1990),
who reported that petroleum generation from kerogen is approx. 90% com-
plete for temperatures in the range 170-190 °C and heating rates between 0.53
and 5.3 °C Ma- 1 (see Fig. 4.8), it appears that oil generation and destruction
are separated from one another in time and space, rather than gradually
merging from one to the next as the classical oil window concept might infer
(see Tissot and Welte 1984). This point has previously been illustrated by
Sweeney et al. (1987).
The stability of oil might have been overestimated by the kinetic model in
quantitative terms because compositional considerations indicate that as much
as 15% of the original petroleum may have been converted into gas. The high
stability predicted by the kinetic model may in part be related to the fitting of
the spline function to the gas generation curves. To date we have optimized the
whole of each gas generation profile. While this approach has been successfully
applied to oil generation studies using open -system pyrolysates (e.g., Schaefer
et al. 1990), it may not be ideally suited for assessing the onset of oil to gas
cracking. Determining the onset, rather than peak, of oil to gas cracking is very
important in the general case because, depending on P-V-T conditions, only a
small conversion may be required to result in the formation of a separate gas
phase and the displacement of the liquid phase to shallower structures. Opti-
mizing the fit for the first third of gas generation profile may therefore prove
critical in evaluating oil versus gas prospectivity. Sensitivity analysis revealed
that the predicted high stability of the 33/9-14 oil is not tracable to analytical
artefacts and errors.
If the rate of oil to gas cracking depended strongly on pressure, it would be
invalid to extend low pressure experimental studies to geological conditions.
This aspect must therefore also be considered. The maximum pressure attained
in these experiments was estimated to be 3 MPa whereas the pore pressure in
the 2/4-14 reservoir is estimated to be 65 MPa. If increased pressure were to
lead to a reduction in the rate of catagenetic change, as reported by Brooks et
al. (1971), Domine (1991) and Price and Wenger (1992), low pressure ex-
periments would overestimate the rate of oil cracking. Conversely, applying the
results of Fabuss et al. (1964) on hexane cracking, cracking rates may be faster
by 5- to IS-fold at 65 MPa in comparison to 3 MPa. Horsfield et al. (1992)
found no evidence to suggest that pressure has reduced the rate of oil con-
version. In fact, judging by the high stability of oil predicted by the kinetic
model on the one hand and evidence of approx. 15% conversion from com-
positional data on the other, the converse might be true, with pressure having
slightly accelerated the rate of oil cracking. Unfortunately, given the un-
certainties in geological input data to the kinetic model (temperature and
burial histories) and sample representativity inherent to such studies, pre-
264 H.J. Schenk et al.
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Chapter 5
Deposition of Petroleum Source Rocks
Chapter 5: Overview and Insights
5.1
Introduction
It has been long recognized that fine-grained sediments of both siliciclastic and
carbonate compositions are the principal source rocks of petroleum. The
common coincidence of significant, and often high, content of organic matter
within such sediments, as first comprehensively documented by Trask and Wu
(1930), provided the initial clue and support for this now generally accepted
opinion.
Subsequent studies by petroleum geochemists and organic petrographers
have largely confirmed and greatly expanded and quantified this view. Cur-
rently the assessment and evaluation of the petroleum-generating capacity, i.e.,
"potential" of a source rock, is based on the quantity and quality of its organic
matter content. Chemical analysis of the amount (concentration) of total or-
ganic carbon generally provides the basis for quantitative assessment, although
estimates of volumetric amounts of organic matter by petrographic methods
serve as well. Qualitative evaluation is more complex and depends considerably
on the interpretive views of petroleum generation. From a chemical viewpoint
hydrogen-rich organic matter is considered to have the greatest potential for
oil generation, whereas rocks with terrigenous organic matter of low hydrogen
content are viewed as gas prone. Methods to study the quality of organic matter
with respect to petroleum generation are discussed in the textbooks of Durand
(1980), Stach et al. (1982), and Tissot and Welte (1984).
The deposition of sediments rich in organic matter (C org roughly greater
than 1%) is usually restricted to marine and lacustrine sub aquatic environ-
ments in which organic matter is produced faster than it can be destroyed
(Tourtelot 1979). Recent marine environments generally have in common that
they are situated near land, i.e., less than a few hundred kilometers away from
at least one coastline (Kruijs and Barron 1990), and that bottom waters are
IInstitut fUr Erdal und Organische Geochemie (ICG-4), Forschungszentrum Jiilich GmbH,
52425 Jiilich, Germany
2Department of Geology and Geophysics, The Wiess School of Natural Sciences, Rice Uni-
versity, Houston, 77251 TX, USA
3 Institut fUr Chemie und Biologie des Meeres (ICBM), Universitat Oldenburg, Carl-von-Os-
sietzky-Str. 9-11, 26111 Oldenburg, Germany
5.2
Production and Preservation of Organic Matter
5.2.1
The Debate
The opinion that bottom water "stagnation," i.e., oxygen deficiency, anoxia,
has played an important role in the preservation of organic matter and hence
in the formation of organic matter-rich sediments, for example, black shales,
has been a part of sedimentological thinking for many years. However, only
recently, when large amounts of stratigraphic, sedimentological, and geo-
chemical observational data on modern oceanic sediments [e.g., Deep Sea
Drilling Project (DSDP), Ocean Drilling Program (ODP)] and correlative
oceanographic data became available and could be evaluated and interpreted,
was it possible to place some constraints on the causes for the development
and persistence of anoxia in depositional environments. In particular the
synthesis by Demaison and Moore (1980) has proven to be a most influential
analysis of the problem and has provided a landmark for the evaluation of the
role of anoxia in source rock deposition. Currently two contrasting models
(Pedersen and Calvert 1990; Demaison 1991; Pedersen and Calvert 1991) are
used to explain the deposition of sub aquatic, fossil, organic matter-rich sedi-
ments. These are called below the "preservation model" and "productivity
model" (Fig. 5.1; Thunell et al. 1984).
Emphasis on the accumulation of organic matter in sediments and sedi-
mentary rocks has led to a generalized (and somewhat simplified) view that
organic matter productivity and its preservation are the two dominant controls
of the deposition of source rock facies. This viewpoint was emphasized by
Curtis (1980) in her statement that "many geographic settings are favorable for
high organic productivity, but preservation of organic materials requires a
setting where rapid oxidation cannot take place .... " The relative importance of
these two general controls is currently being actively debated. For example,
Stein (1986a) in his discussion of black shale deposition in the Mesozoic
276 R. Littke et al.
048
,--::> Aerobic
~(mlll)
Anaerobic
Upwelling zone
5 -------------
5------- __ ~
O2 (mill) ,
Fig. S.IA,B. Generalized models for the deposition of organic matter-rich sediments.
A Stagnation model for anoxic silled basins. B Productivity model for upwelling regions.
(Modified from Littke and Welte 1992; Thunell et al. 1984)
Atlantic Ocean notes that "the genesis of these sediments can be explained by
(1) high flux rates of marine organic matter in areas of high oceanic pro-
ductivity, (2) high flux rates of terrigenous organic matter, and/or (3) increased
preservation of organic matter in areas of anoxic deep-water environments as
well as due to rapid burial of organic matter... " and that "which of these
different mechanisms is more or less important for the origin of black shales is
still open and controversial." Recently, enhanced preservation of organic
matter adsorbed to mineral surfaces has been discussed as an additional, and
possibly important, control on organic matter accumulation in sediments
(Collins et al. 1995).
Advocates of the importance of productivity, Le., the supply of organic
matter, including Calvert (1987), Pedersen and Calvert (1990), and Bailey
(1991) argue cogently that "sporadic temporal and spatial increases in primary
production, reflecting changes in the behavior and/or state of the ocean-at-
mosphere system ... constitute a more tenable explanation for the occurrence of
modern and Quaternary carbon-rich sediments and Cretaceous black shales,"
and that "consequently, the fundamental control on the accumulation of car-
bon-rich facies in the oceans and marginal seas is not the presence or absence
of anoxia." In this view suitable preservation conditions, for example, low-
oxygen bottom waters, "are the result of the high production" (Calvert 1987,
p. 146) and due to the high oxygen demand of the settling organic matter.
Deposition of Petroleum Source Rocks 277
Table 5.1. Terminology for low oxygen regimes and the resulting biofacies. (Tyson and
Pearson 1991)
The authors suggest that the boundary between suboxic and dysoxic conditions marks the
limit for bioturbation (see Savrda and Bottjer 1991) and nitrate reduction.
278 R. Littke et al.
5.2.2
Some Observations
mainly coastal waters. Because of changing land mass distributions and cli-
matic conditions both magnitude and global pattern of oceanic organic matter
production are likely to have changed considerably during the geological
history of the earth (Arrhenius 1952).
Muller and Suess (1979) used a relationship between organic carbon content
of sediments and sedimentation rate to obtain Pleistocene productivity data for
open ocean conditions. After calibrating with data for the present ocean, they
arrived at an empirical equation for paleoproductivity (PaP, in g Cm-2 y-l):
PaP = Co(1 - <jl) /0.003 S03
where C is the percentage of organic carbon, 0 is the dry sediment density, <jl is
the porosity (as a fraction of the volume), and S the bulk sedimentation rate.
They thus suggested that productivity can simply be estimated from the or-
ganic matter content of a sediment using a fraction of the sedimentation rate
for correction. Paleoproductivity calculation must be regarded, however, as an
estimation rather than an exact quantification procedure because several im-
portant parameters are neglected. For example, different classes of phyto-
plankton have vastly different labilities upon oxic and anoxic decay, as
demonstrated by the often excellent preservation of green algae such as
Bottryococcus and Tasmanales or of dinoflagellate cysts and by the limited
degree of preservation of organisms with siliceous and carbonate shells such as
coccoliths (e.g., Littke et al. 1991b). In addition, total organic carbon contents
in sediments depend on factors such as oxygen and sulfate availability during
early diagenesis, which can hardly be incorporated into this type of formula.
Nevertheless, some useful refinements and applications have been published
on paleoproductivity estimates.
It has been shown that the organic carbon accumulation rate is a function of
carbon flux near the sea floor, which in turn is related to the productivity and
the water depth. Using flux information of Betzer et al. (1984), Stein (1986a,
1991) derived the following more complex empirical relationship for estimat-
ing paleoproductivity:
PaP = 5.31[C(owB - 1.026<jl)]071S0.07D045
with 6WB = wet bulk density and D = water depth. Values calculated this way
are linearly related, although not numerically identical to values obtained from
another empirical equation by Sarnthein et al. (1987, 1988):
PaP = [15.9342C . S . o( 1 - <jl) ]06590 . SB-C -07143 . DO 3174
where SB-C is the organic-carbon-free bulk sedimentation rate.
Applying their simple relationship to sediments from offshore northwestern
Africa, Muller and Suess (1979) found that Pleistocene productivity in the
ocean was about the same as today during interglacial stages but higher by a
factor of up to 3 during glacial times, due mainly to more intense upwelling or
mixing of water masses. In a high-resolution stratigraphic study for the last
500000 years in the same area, Sarnthein et al. (1987, 1988) found the same
range of productivity fluctuations in upwelling sediments with their more
sophisticated equation; the productivity amplitudes were much less pro-
280 R. Littke et al.
Table 5.2. Estimates of paleoproductivity for different time intervals at upwelling site 658 and
nonupwelling site 659 offshore West Africa. (Modified after Stein et al. 1989)
Depth Age Wet-bulk- Porosity Mean sed. Total organic Marine organic Paleoproductivity
(mbsf) (Ma) density rate carbon content carbon content
(g cm- 3 ) (% ) (cm 1000 a-I) (% ) (% ) II
Site 658
0-100 0-0.7 1.65 68 14.7 a: 1.61 1.05 190 150
b: 1.26 0.82 160 130
100-174 1.6-2.45 1.60 62 7.2 a: 2.13 1.38 240 210
b: 1.81 1.18 220 190
174-240 2.45-3.1 1.60 62 10.8 a: 1.99 1.29 240 200
b: 1.67 1.09 210 170
240-295 3.1-3.6 1.73 56 10.8 a: 2.54 1.65 320 260
b: 1.49 0.97 220 180
Site 659
0-50 0-1.6 1.51 68 3 0.22 0.15 40 50
50-135 1.6-4.5 1.60 64 3 0.15 0.10 30 40
135-230 4.5-8.5 1.74 56 0.3 0.D7 0.05 20 30
For the time interval from 0-2.45 Ma at site 658, a is interpreted as glacial and b as interglacial
stages based on different carbonate contents. Paleoproductivity calculations are based on: I,
Stein (I986a); II, Sarnthein et al. (1987).
Fig. 5.2. Paleoproductivity (in gC m- 2 y-l) calculated for times of mudstone/limestone de-
position (A) and times of black shale deposition (B) for DSDP sites in the eastern Atlantic
Ocean. Underlined values, calculated using the paleoproductivity equation modified by Bra-
lower and Thierstein (1987) for anoxic deep-water conditions. (Stein 1986a)
Deposition of Petroleum Source Rocks 281
I 23 90 31 ~,
- .. v _ I
I
3L
- HIATUS
• •• HI
ATUS'
( IINFLI£I'C:E OF
31 I 33 1£>'1 33 21 T~BlOITES
32 lDB
31
,
I 11091 -
102 -
" NO MARI/oE Corg
I
1 119 155 170 - 00 = 1 126 - -
171 v 38 52
50
22
NO<Otrltrl1"-1Q
U")OOcnM""~
tf')~""M 1.11"'....,.
HOltT",."
A NOAtM .AllANf.e.
I ~,
- HIATUS
I · · · IiIATUS ?
I I IINFL1£I'C:E OF
I 168 14401 T~eIlJlTES
" NO MARINE Corg
2.6 7, _ (~I
19 18 ~I li 62
3 11 ~ Zil JlI
(16 1 " 74
...
"
B HOA'Utr_ ...
MOlltTH All"IIIT.C.
NoafN A, " A III " " SOUTH 1.U"UlTlt
282 R. Littke et al.
50
50
10
10
5
C org
(% )
0.5
~ 657
m 6SS
0.1 0. 1 659
50 CENOMANIAN I TURONIAN
10
C...
(%)
O.S ~
8l.ACK SHALE •
MI.IOSTONE.. CHALK D
~
BLACK SUAU: •
MUDS'TON[.Ctw..K 0
0.1 ~lillC
8l.AClt: SHALF. ""
0,05 +-__--+_+-__--1_-+-_-"c.:=c:.:.:,F-;;:.F..c;;;;""f'o';...-"-v
N
Fig. 5.3. A Correlation between (marine) organic carbon and sedimentation rates. The dis-
tinction between fields A, A', and B is based on data derived from Recent to Miocene sedi-
ments deposited in normal open-ocean environments (field A), upwelling high-productivity
areas (field A'; stippled area, coastal upwelling and the open area at the lower end of field A'
indicating equatorial upwelling data) and anoxic environments (field B). From Stein (1990;
modified after Stein 1986b). B Organic carbon vs. sedimentation rate diagram applied to
sediments from ODP sites 657-659 offshore West Africa. Site 657: 1, Pliocene-Pleistocene
(0-4.5 Ma); 2, latest Miocene (6-7 Ma); 3, late Miocene (7-8.5 Ma). Site 658: 1, Pleistocene
(0-0.7 Ma); 2, latest Pliocene (1.6-2.45 Ma); 3, late Pliocene (2.45-3.6 Ma). Site 659: I, Plio-
cene-Pleistocene (0-4.5 Ma); 2, late Miocene (4.5-8.5 Ma); 3, late Miocene 8.5-10 Ma. From
Stein et al. (1989). C Organic carbon vs. sedimentation rate diagram applied to Cenomanian/
Turonian sediments from the Atlanic Ocean. (Stein 1986b)
284 R. Littke et al.
5.3
Transport of Organic Particles
Table 5.3. Sinking velocity, travel time (through 1000 m water), and lateral transport
distance (at a current velocity of 1 mm/s and 100 m water depth) for spheric particles
in nonturbulent water. (See von Engelhardt 1973)
Densities of coal macerals usually vary between 1.1 and 1.7 g/cm3 (van Krevelen
1961).
286 R. Littke et al.
20 Site7S4
J~
Mllestrichim
(IDdian Oc:em)
60 Site 64S
10 (Baffin Bay)
I~
~
iz 0
5
~30
0 5 10 15 20 2S 30 35
Lea8tb(pm> j 15
z
Site 755
Pre-Maeatricbian 5 10 15 20 2S 30 35
Lea8tb(pm>
J=
~30
(Indian Oc:em)
j: 70
60
Kimmeridge
(NOl1hSea)
0
0 5 10 15 20 2S 30 35 ·1 SO
Lea8tb(pm>
j40
fO Site 758
Pre-Maestrichim j:
j 5
(Jndian Oc:em)
10
~
40
j
0
0 5 10 15 20 2S 30 35 4S SO
Lea8tb(pm>
5 10 15 20 2S 30 35
Lea8tb(pm>
Fig. 5.4. Histograms of length of terrigenous organic particles (vitrinites and inertinites) at
sites 754 and 755 (Broken Ridge, Indian Ocean), 758 (Ninetyeast Ridge, Indian Ocean), 645
(Baffin Bay, i.e., near land, see Stein et al. 1989), and in the Kimmeridge Clay in the North Sea
(Brae Field; see Leythaeuser et al. 1988). The particle size is related to the distance of trans-
port. (Littke et al. 1991 c)
small grain sizes seem to be typical for open marine sediments, providing no
turbidite transport (see Degens et al. 1986) affected deposition. In contrast,
shallow marine or deep water, continent-near deposits such as the Kimmeridge
Clay from the Brae Field, North Sea, contain particles of 50 11m diameter and
greater (Fig. 5.4). Even larger grain sizes are found in fluvial-deltaic sediments
deposited under humid climatic conditions. For example, Upper Carboniferous
siltstones and sandstones of the Ruhr area contain abundant plant fragments of
several millimeters length (Scheidt 1988).
The observations on grain sizes of allochthonous organic particles in dif-
ferent environments indicate that transport of organoclasts leads to mechanical
grain size reduction and sorting of grains according to size with increasing
distance of transport or transport energy in very much the same way as well
established for mineral grains. In general, large transport distances of orga-
Deposition of Petroleum Source Rocks 287
Back-Arc Basins
"\ u r 6
~ .,-
0'
,,-
I'
Fig. 5.5. A,B Percentages (of total macerals) of vitrinite, inertinite, and liptinite from different
deep sea environments. (Littke and Sachsenhofer 1994)
288 R. Littke et al.
noclasts are favored by their low density compared to mineral grains. This also
leads to large residence times of organoclasts in the water.
While large transport distances of terrigenous organoclasts compared to
terrigenous mineral matter lead to a relative enrichment of the former, it is
unlikely that transport sorting causes deposition of layers rich in terrigenous
organic matter at distal sites in the oceans because more and more auto-
chthonous siliceous and calcareous marine particles are admixed. It is also not
expected that liptinite-rich sediments evolve from transport sorting, although
liptinites (hydrogen-rich organic particles) have a lower density than vitrinites
and inertinites. Liptinites are, however, more susceptible to degradation than,
for example, inertinites and therefore if transportation is of long duration less
well preserved. This is the reason why in most marine sediments deposited
under oxic bottom waters terrigenous organic particles (resedimented vi-
trinites and inertinites) predominate over marine particles (alginite; Littke and
Sachsenhofer 1994).
Generally, with increasing distance of transport, the inertinite/vitrinite ratio
increases, indicating a greater degree of chemical degradation. In many coals as
well as in many lacustrine, fluvial, deltaic, and shallow marine deposits, vi-
trinite is the most abundant organoclast (e.g., Horsfield et al. 1988), but in most
open marine deposits inertinite predominates (Fig. 5.5; Littke and Sachsen-
hofer 1994). The latter is known to be the product of a more severe degradation
of terrigenous organic matter, whereas vitrinite derives from a less severe
degradation of the same principle precursors (Stach et al. 1982; Styan and
Bustin 1983). It is an open question why at least some small vitrinite is pre-
served in open ocean sediments derived from slow deposition under well-
oxygenated bottom water, i.e., under conditions favorable to a strong de-
gradation of organic matter.
5.4
Deep Marine Silled Basins
Demaison and Moore (1980) identified anoxic silled basins as a major setting
for marine oil source rocks and discussed the Black Sea as a typical con-
temporary example. In anoxic silled basins the major control on deposition of
organic carbon-rich sediments is anoxicity of bottom water and pore water
leading to high ratios of preserved over produced organic carbon (Bralower
and Thierstein 1987). Although they acknowledge the importance of several
other source rock depositional controls, for example, primary biological pro-
ductivity, biochemical alteration of dead organic matter, transport time and
mechanism, and the effect of sediment particle size and sedimentation rate,
clearly their view places considerable importance on the existence of anoxic
conditions and its resultant enhancement of organic matter preservation.
Simply stated, they note that "anoxic conditions occur where the natural de-
mand for oxygen in water exceeds the supply," or more explicitly, where de-
gradation of organic matter depletes the oxygen supply, which results in anoxia
unless associated circulation of aerated water masses renews the oxygen sup-
ply. Because of common restrictions to water circulation, for example, strati-
Deposition of Petroleum Source Rocks 289
I ....--
50 50
• Areo ofhigh product/rily
• •
10. . ; .i 10
•
5 .1 • 5 .,,~
•
lIj;J:· · '":
t
"#
• • •• ••
·
u •• • t t •
••
I I
• ~f.i~·
u
• 0.5
•.
: f.· 0.5
c
.,
...
CD
......
•••
•
01 0..1
00.5 0.0.5
OXIC BOTTOM WATER ANOXIC BOTTOM WATER
0..0.1 0.0.1
0..1 0.5 I 5 10. 50. 10.0. 0..1 0..5 5 10. 50. 100
SEDIMENTATION RATE lell!1 ODD,! •
Fig. 5.6. Relationship between organic carbon content and sedimentation rate in recent and
Quaternary sediments. (Huc 1988b after Stein 1986a; Pelet 1983)
Deposition of Petroleum Source Rocks 291
shale sedimentation existed at that time in parts of the oceanic basin which
were closed (silled) with small rates of water circulation such as in the young,
opening Atlantic Ocean. Organic carbon percentages are highly variable in
these sediments and reach maximum values greater than 20%. However, the
petroleum generation potential of the kerogen is not particularly high, i.e.,
hydrogen index (HI) values do not generally exceed 600 mg hc/g Corg and are
often much lower. Petrographically the organic matter is mainly unstructured
without any primary biological aspects even when studied under high mag-
nifications by transmission electron microscopy or scanning electron micro-
scopy. A strong microbial degradation of the original marine biomass is the
likely cause of these maceral characteristics and possibly also of the relatively
low HI values compared to shallow marine and lacustrine petroleum source
rocks (Littke and Sachsenhofer 1994).
In summary, deep, marine, silled basins are characterized by a small water
exchange between surface and bottom waters. Often there is a narrow zone
within the water column in which the physical and chemical characteristics
such as temperature, density, salinity as well as oxygen and hydrogen sulfide
concentrations change abruptly. Below this narrow zone anoxic bottom waters
and pore waters persist in which organic matter degradation is restricted to
anaerobic processes (probably mainly to microbial sulfate reduction; see
Chap. 5.7). Sediments in these environments are often rich in organic carbon,
similar to those from lakes with small water circulation.
100
~'• 100
Neogene
••
200 Oligocene 200
300
Paleocene • 300
,.,
~
-r:
~
k··
..
400 .+ +
400
Cretaceous
500 +
+
++ 500
600 600
o 100 o
CaC03 (%)
Fig. 5.7. Carbonate and organic carbon percentages in Cretaceous to Holocene sediments of
ODP site 758, northern Ninetyeast Ridge, Indian Ocean. The decrease in carbonate and in-
crease in Corg in the upper 100 m is an effect of the enhanced detrital supply to the Bengal fan
(Ganges and Brahmaputra) which itself is a response to the ongoing rise of the Himalayan
mountains. In other words, the source of organic particles became more proximal with in-
creasing progradation of the Bengal fan. Higher Corg values in the Cretaceous are affected by
supply of terrigenous organic particles in the then smaller Cretaceous Indian Ocean. (Littke et
al. 1991c)
292 R. Littke et at.
5.5
Progradational Submarine Fans
Distance, distance between river (delta) mouth and depositional site; water depth, present
water depth; Corg , mean organic carbon percentage; HI, mean and maximum (in parentheses)
hydrogen index value; Origin, origin of organic particles based on microscopy and/or
geochemical results. Sites 615 and 620 according to Marzi and Rullki:itter (1986); site 720
(upper 150 m, Pleistocene), and 721 (upper 100 m Pleistocene and Late Pliocene), according
to Prell et al. (1989), site 758 (upper 30 m, Pleistocene and Late Pliocene), according to Peirce,
Weissel et at. (1989).
Deposition of Petroleum Source Rocks 293
5.6
Upwelling Areas
Upwelling areas are regions in which great masses of oceanic surface waters
move offshore and are replaced by oceanic deep water. The upwelling process
is driven by either atmospheric or ocean forcing mechanisms such as wind,
coastal currents, and the Coriolis force (Suess and Thiede 1983). Upwelling
rates are calculated from surface wind stress and the Coriolis force (Kruijs and
Barron 1990) and range from close to 0 to more than 20 cm per day. The
294 R. Li ttke et al.
upwelling deep waters are often enriched in nutrients such as nitrate, phos-
phate, and silicate (Baturin 1983; Bishop 1989) thus favoring high primary
productivity rates (greater than 180 g C m- 2 a-I; see Berger et aL 1989a,b) in
surface waters and oxygen shortage in waters below the photic zone (Fig. 5.1).
Areas of high primary productivity occupy only a very small proportion of the
modern oceans (Berger 1989) and are often related to upwelling. Baturin (1983)
estimated that the total area of recent strong upwelling is only 500000 km2 or
about 1%0 of the world ocean. Prominent upwelling cells are situated offshore
the coasts of northwestern Africa, southwestern Africa, Peru, northwestern
North America, Oman, and in the equatorial Pacific. The processes influencing
sedimentation in upwelling areas are described in great detail by Thiede and
Suess (1983), Suess and Thiede (1983), and Summerhayes et aL (1992). Typical
features of sediments underlying upwelling areas include (1) high organic
carbon (2-20%), (2) high biogenic silica (5-70%), (3) elevated phosphorus
(0.2-1%) contents, (4) high rates of biogenic sedimentation (up to 0.5 mm/a),
and (5) the occurrence of coprogenic material (Baturin 1983). Petrographically
the upwelling sediments often contain predominantly unstructured organic
matter with only a small contribution of algal remains resembling the primary
biomass and only little terrigenous organic matter (Littke and Sachsenhofer
1994; Liickge et aI., 1996). This observation, together with the rather low hy-
drogen indices, is taken as an argument for a restructuring of the primary
biomass due to degradation processes before and shortly after deposition.
Organic carbon accumulation in upwelling areas does not depend solely on
primary productivity related to upwelling but also on the interaction of the
upwelling system with the topography of the shelf and continental slope (Re-
imers and Suess 1983; Kruijs and Barron 1990). This is supported by Baturin
(1983) who suggested that unfavorable conditions for accumulation of organic
matter-rich sediments persist where there occur steep shelf platform
morphologies, high energy wave climates, strong bottom currents, high rates of
terrigenous sedimentation, bioturbation by bottom fauna, and repeated
transgressive/regressive cycles (erosional events). Three examples from the
upwelling areas, offshore northwestern Africa, Oman, and Peru, illustrate the
influence of various factors on organic matter accumulation.
An upwelling area below which sediments are not particularly enriched in
organic carbon is the northwestern African shelf at ODP site 658 (Table 5.5;
Stein and Littke 1990), where organic carbon contents generally vary between
1% and 3% and do not exceed 4%. Furthermore, HI values from Rock-Eval
pyrolysis are relatively low (Stein et aL 1989). This is explained by the oc-
currence of greater amounts of terrigenous organic matter than at other up-
welling sites (Littke and Sachsenhofer 1994). In other upwelling areas the bulk
of the organic matter stems from bacterially degraded phytoplankton, and
terrigenous organic matter contributes only a small proportion to the total
organic matter (Summerhayes 1983; ten Haven et aL 1990).
Higher organic carbon contents than offshore northwestern Africa are re-
ported from the upwelling area of offshore Oman (Tables 5.5, 5.6; Prell et al.
1989). Figure 5.8 shows an idealized cross section through the continental
margin off Oman with the position of six different wells drilled by the ODP.
Deposition of Petroleum Source Rocks 295
Table 5.5. Average organic carbon percentages, average HI, bulk sediment (ARBS), and or-
ganic carbon accumulation rates (AROC)
From sediments on the continental margins at site 658 (Pliocene to recent; Stein and Littke
1990), at site 723 (Pleistocene to recent; Prell et aI. 1989), and site 679 (Quaternary; ten Haven
et al. 1990).
One of the sites (725) is situated at the very top of the oxygen-minimum zone
which underlies the surface water. Two sites are just within the oxygen mini-
mum zone (723 and 72S), two are on the Owen Ridge and just below the oxygen
minimum zone (731 and 722), and one is outside the upwelling area in the deep
sea and affected by the Indus fan (720). Organic carbon contents and HI values
of the uppermost sediments from these sites are summarized in Table 5.6 (after
Prell et al. 1989; ten Haven and Rullkotter 1991). Organic carbon percentages
and HI values are greatest in sediments deposited within the oxygen minimum
zone, i.e., at water depths which exceed 350 m but are less than 2000 m. Even
there only about 1-3% of the primary organic carbon production in surface
waters is preserved in the sediments; more than 97% was lost due to re-
mineralization (Liickge et aI., 1996). Shelf sediments deposited in relatively
shallow water like those drilled at site 725 (311 m) contain little organic matter
which is characterized by low HI values. Most favorable conditions for organic
matter deposition occur where sedimentation takes place in the upper part of
the oxygen minimum layer, for example, at site 723 at a water depth of S07 m.
Table 5.6. Depth intervals (meters below sea floor, mbsf), stratigraphic age, average organic
carbon contents, average HI, accumulation rates for bulk sediment (ARBS), and accumulation
rates for organic carbon (AROC) for the uppermost intervals drilled at ODP sites offshore
Oman (see Fig. 5.8). (Prell et aI. 1989; ten Haven and Rullkiitter 1991)
Note that average Corg and HI values are tabulated for the depth interval only, while
accumulation rates are calculated for the entire Holocene-Pleistocene section (see also Littke
1993).
296 R. Littke et aI.
High producllvlly
2 .---. associated wdh
seasonal upwelling
water
1'" ..........
~ » ~ ,. 'P ,..
. . ,. ......... . .1 "
~ ~.J.
:;x:/.:r<.
, ..: , 'J ,. ... ., ...
~ ~o?t/ :>
3
",<: :
Jo 1 )0 ... ... C ,. ... 1'" ....... ,..
,) .. .. ., ,. ... c........
... 01< .I"
c ... ." r
r _ 't-.:=~
, r --
Oman Margin Owen Ridge Indus Fan
Fig. S.B. Idealized transect of the continental margin off Oman showing major geological and
oceanographic features and locations of sites discussed in text (vertical scale exaggerated).
(Spaulding 1991)
For these sediments the average HI value is about 300 mg hc/g Corg. This value
is greater than those established for the other sites on the Oman continental
margin but still lower than for many ancient petroleum source rocks. Favorable
conditions for the deposition of organic matter-rich sediments also occur
where the sediment/water interface is within the lower part of the oxygen
minimum zone or slightly deeper as at site 722 (about 2000 m). Sediments
deposited in the deep sea as at site 720 (about 4000 m water depth) contain
lower average organic carbon contents and have low HI values. The occurrence
of mass flow or turbidity current sediments at these deep locations causes few
exceptionally high organic carbon values and is responsible for the high
standard deviation recorded in Table 5.6.
The upwelling system offshore Peru serves as another example of the
complexity of sedimentation patterns in these depositional environments. In
upwelling areas the distribution of organic carbon-rich deposits is not only
controlled by primary productivity but also by current activity and ocean floor
morphology (Reimers and Suess 1983). This is evident from Figure 5.9, which
compares primary productivity rates in surface water and organic carbon
percentages of the uppermost sediments for the Peruvian coast. In general,
bioproductivity is most enhanced and rather homogeneously distributed along
Deposition of Petroleum Source Rocks 297
the coastline and becomes successively smaller towards the open ocean. Or-
ganic carbon percentages of surface sediments are exceptionally high in two
small areas between II ° and 14° S, but lower towards the north, although
upwelling intensity and bioproductivity are in the same range. Reimers and
Suess (1983) explain this difference by shallower water depths between 7° and
10° S, which promote continuous reworking by bottom currents and inhibit
sedimentation.
Furthermore, the data from the Peruvian upwelling system nicely illustrate
that high Corg contents do not necessarily coincide with high organic matter
accumulation rates. Table 5.7 compares Corg and HI values and accumulation
rates of a site at about 11 ° S (area of high Corg contents) and of a site at about
14° S (area of high accumulation rates). Offshore Peru, high Corg percentages
coincide with high HI values, whereas high accumulation rates do not coincide
with high HI values. These data further support that in oxygen-deficient bot-
tom water environments the general rule of a positive correlation between
organic carbon percentages and sediment accumulation rates finds its excep-
tion (Fig. 5.3).
Comparisons between the occurrences of upwelling, on the one hand, and
high primary productivity, on the other, reveal that: (1) upwelling is the most
common but not the only cause for high bioproductivity rates; another source
of nutrients is river discharge (van der Zwaan and Jorissen 1991); (2) many
upwelling areas (82% according to Kruijs and Barron 1990) are not associated
with high productivity rates or high Corg percentages of underlying sediments,
especially in the open ocean; it is only along coastlines that a strong positive
correlation between upwelling and high productivity and Corg percentages
(Kruijs and Barron 1990) is observed; this may also be due to the additional
nutrient supply from land and to favorable topography of the sea floor.
B
Total primary production SedimenlAry organic
(gC m-2 day- I) carbon (weigbt-%)
• >10
5-10
2.5-5
Fig. 5.9. Total primary production (A) and sedimentary organic carbon in surface sediments
(B) in the upwelling area off Peru. (Redrawn after Reimers and Suess 1983)
298 R. Littke et al.
Table 5.7. Depth intervals (meters below sea floor), age intervals (million years, Myr), average
organic carbon contents, average HI, accumulation rates for bulk sediment (ARBS), and
accumulation rates for organic carbon (AROC) for the youngest sediments in Holes 680B and
686B, offshore Peru
680 (11 OS) 260 0-41 0-0.62 5.34±2.57(47) 506±177(46) 3.7 0.20
686 (14 OS) 450 0-160 0-1.41 2.32±1.36(8) 334±78(8) 19.6 0.45
Accumulation rates are corrected for the hiatus between 0.62 and 1.37 Myr at site 686 (Wefer
et al. 1990). Corg and HI data are from Suess et al. (1988; site 686) and Emeis and Morse (1990;
site 680), age information is from Wefer et al. (1990) and sediment densities are from Suess et
al. (1988). Corg was measured by the Rock-Eval method.
5.7
Anoxic Continental Shelves
Black shales which are deposited in shallow marine environments are common
in the Palaeozoic and Mesozoic ancient geological record, but there is no well-
documented modern analogue (Hallam 1981, p. 90). Late Carboniferous black
shales of Europe and North America are discussed here because they are re-
garded as well-studied examples of these organic matter-rich continental shelf
deposits (Wenger and Baker 1986; Heckel 1991). They clearly represent
transgressive phases within the Carboniferous sedimentary sequence in which
they are sandwiched between nonmarine and marine facies including lime-
stones above. As these thin (usually 1 m and less) black shales lack any benthic
fossils and any evidence of bioturbation (O'Brian 1990), it is concluded that
they were deposited under anoxic conditions (see Table 5.1).
A geochemical profile through one of these Pennsylvanian black shales
(maturity corresponds to 0.54% vitrinite reflectance) is shown in Figure 5.10.
Organic carbon contents are high (17%) at the base of the black shale and
decrease toward the top. HI values are also greatest at the base (320 mg hc/g
Corg ) but not particularly high if compared to other immature black shales.
t:)
(!)
Deptb (ft) J , "0
s· 0
185 ~.
. o·
::;
I
·..,.
.., 0
....,
a r
r· a '"0
... .i
186 -I a
. f. '- ...
0 ..t" ...0~
0 .".
r ~
ro
~
0
: ~
. .. :-. a
0 C/>
• ! 0
~
..-: ,.. .
\'" .....
0 ...
.. r-,
I (!)
0
." .
18'1· D ;,.' :>:J
0
.. -.-... (")
~
D : . en
,
.:
0 ' '
. '
. '...
1881· D
.
D . -.-.
189 .,_ D :1'
...'. ...1:.
B . " .. ..
0
D
. .. · ...
190 -I 1'
D I..
t .. '."
D : ~ I.. .. ....
191 -I
0
~ 2• ~ 810
i i
.
Total S (% )
192 I i i i i i i
0 2 4 0 14 28 0 10 20 0 20 40 60 0 10 20 0 100 200 30C 400
Vitro + Inert. Bituminite Alginite (% ) Carbo (%; squares) Org. C (%) m (mg HClg Org. C) N
(see text) \0
+ Spor. (% ) \0
Fig. 5.10. Geochemical and petrological profile through a core of the Little Osage Shale (Upper Carboniferous) from a well in
northwestern Oklahoma, United States (Rr = 0.54%). Carb., carbonate (Part of the data are from Wenger and Baker 1986)
300 R. Li ttke et al.
This pattern of an abrupt increase in Corg and HI values at the base of black
shales and a more gradual decrease towards the top was also observed in other
black shales (e.g., Piasecki and Stemmerik 1991). For the Pennsylvanian black
shales, maceral analysis revealed that the organic particles are a mixture of
fluorescing alginite probably derived from marine phytoplankton and of
brightly reflecting, weakly or nonfluorescing particles. The presence of the
latter material is expected to cause the relatively low HI values of these black
shales. Low HI values are generally typical for terrigenous organic matter, and
the "bright particles" were initially proposed to be derived from peat clasts
(Wenger and Baker 1986). However, molecular geochemical data and organic
petrographic observations (such as the lack of phenols in pyrolysis products
and the lack of trimacerites) do not support a terrigenous organic-clast origin;
an explanation as hydrogen-poor humic precipitate is more realistic. The
precipitation of humic acids is favored in environments where water mixing,
for example, mixing of saline water with freshwater, occurs (Swanson and
Palacas 1965; Lyons et al. 1984). Such a mixing is certainly not improbable
during the time of Pennsylvanian black shale deposition.
The organic richness of many thin shallow marine sedimentary rocks which
occur in coal-bearing fluviodeltaic strata suggests a common controlling me-
chanism and depositional model. Wenger and Baker (1986) and Wenger (1987)
suggested that transgressive-regressive cycles are the major control of the ac-
cumulation of the Pennsylvanian black shales of the North American mid-
continent. Rapid transgression of epicontinental seas over laterally adjacent
widespread peat swamps and emergent delta-plain surfaces, formed during the
previous regressive cycle, resulted in leaching of flooded sediments and an
enhanced influx of nutrients and humic materials to the marine environment.
The nutrients stimulated high algal productivity and the terrestrially derived
organic material provided an additional sink for oxygen which enhanced an-
oxia. As transgression proceeded to its maximum, the swamps and delta plain
were progressively flooded and diminished in areal extent, the influx of nu-
trients and humic material decreased, productivity dwindled, intensity of an-
oxia and preservation of organic matter decreased, and black shale deposition
terminated. Subsequent regression led to the reestablishment of delta-plain
surfaces and coexisting swamp environments creating the conditions appro-
priate for the deposition of a succeeding black shale during the next cycle of
transgression (see Wenger and Baker 1986). This evolution is summarized in
Fig. 5.11 and is in accordance with the geochemical data (Fig. 5.10) which
suggest that black shale deposition starts more abruptly than it ends. Similarly,
evidence for the importance of eutrophication of shallow seas by riverine in-
flow of nutrients has recently been published by van der Zwaan and Jorissen
(1991) who concluded that "the chance of anoxia is highest during periods of
high sea level, leading to large shelf areas."
One of the best -studied of all shallow marine Mesozoic petroleum source
rocks is the Lower Toarcian Posidonia Shale, which extends over an area of
more than 300000 km2 in northwestern and central Europe (Table 5.8). The
Posidonia Shale is the source for economic oil accumulations in northern
Germany (Wehner et al. 1989), in the Paris basin (Espitalie et al. 1987), and in
Deposition of Petroleum Source Rocks 301
Kelly 1
~~
MIDLAND
BASIN
I TX OK I KS + MO
________~_______________-~1~
400
~~M~
I~
I
==
ILL IND TO ~PPAL':;L~~-
S__________________-L____--
VERTICAL· HORIZONTAL
SL :'~E~X~TE~N:S:':VE~T~R~A~N~SG;R;E;S;S~IO~N~~~~~~H~M~'C~D~ET~R~';TU~S~~~~~~~~~~
N T
F ---- '
_ _ '....
- - - _- - - - - : - - -".:;.7;,.,.-.. . . --:...,.,,-
-----::;..:;:; ..... / / /
,.,-;;-;:~ ..... / / , . ,
"/' -::. -- f SUBMERGED SWAMP 1
,-.--
/,;'1,/ f-- DEEPER EPICONTINENTAL 5EA - - - - - " 1 I - - - - - SWAMP - - - - - i
4. MAXIMUM TRANSGRESSION
SL - - - - - - - - - - - - - - - -__~~~----------------------~~~ ~
DECREASING HUMIC DETRITUS
& NUTRIENTS
Sl~::::--~.,~~~~~~~~~~~&~N~um~I~EN~T~S;:~~_~~~~~i
Black Shales
NUTRIENTS DEPlETEO
- -; - -- - - -"-~--~~~
____ '/ -/-" ,/'" ...... ......:: .
-,-//-;:'~-;",//'" ,/
Fig. 5.11. Depositional model for transgressive Upper Carboniferous black shales. Inflow from
distal, flooded land areas and the leaching of the former land surface probably provided the
nutrients for enhanced algal productivity and humic matter which substantially intensified
anoxia and led to high organic matter contents in the sediments (see Fig. 5.10). (Wenger and
Baker 1986; Wenger 1987)
....,
o
N
Table 5.8. Regional comparisons of the Toarcian black shales of central and northern Europe
Eastern England 10-33 Shale 5-15 2-5 300-600 Limestone and Jenkyns (1985),
and North Sea av.<I1.4 shell beds Morris (1980)
Northwestern 16-40 Laminated shale avo 11 35-61 600-700 Upper shale, lower Littke and Rullkotter
Germany and madstone madstone units (1987), Littke et al.
(1988)
Southwestern 5-20 Shale and 9-14 av.40 700 8 13C-excursion Kiispert (1982)
Germany madstone; partly
laminated
avo 9 Widespread Urlichs (1977)
limestones
"Anoxic biomarkers" Moldowan et al. (1986)
Paris Basin 10-30 5-14 10-30 Durand et al. (1972)
5-11 20-40 Homogeneous org. Huc (1977)
matter ?'
65 Shale-madstone 4-7 500-700 Espitalie et al. (1987) t-<
Tethys 8-80 Madstone 1-2 <50 200-500 Restricted basins in Baudin et al. (1990) ~
Greece '"~
Laminated shale avo 1.3 200-300 Italian Alps Jenkyns (1985)
~
Deposition of Petroleum Source Rocks 303
parts of the Upper Rhine Valley (Welte 1979). The organic matter from the
Posidonia Shale was defined as the typical type II kerogen (Tissot and Welte
1984). Petrogaphically it consists of a mixture of mostly alginite with an ad-
mixture of bituminite and terrigeneous macerals (Littke et al. 1991a,b), al-
though bituminite may be predominant at some locations (Teichmiiller and
Ottenjann 1977). Geochemically the organic matter is characterized by a high
petroleum generation potential, as documented by HI values in excess of
600 mg hc/g Corg. This type II kerogen, derived from a mixture of phyto-
plankton, zooplankton, and bacteria, is typical of many high-quality petroleum
source rocks which were deposited in shallow marine, reducing environments
(Tissot and Welte 1984). Apparently the degradation of the primary, lipid-rich,
autochthonous biomass is less severe than in deep-water environments.
Nevertheless, part of the metabolizable organic matter is consumed during
early diagenesis in this type of environment. This early diagenetic degradation
is indicated by common high percentages of sulfur in the form of iron sulfides
(pyrite) in shallow marine black shales. Pyrite framboids derived from bac-
terial sulfate reduction and organic matter oxidation are recognized as ubi-
quitous constituents of petroleum source rocks. Sulfur concentrations and
sulfur/organic carbon ratios in shallow marine source rocks are usually higher
than in lacustrine black shales due to the limited sulfate availability in fresh-
water compared to seawater (Berner 1984), and also higher than in organic
carbon-rich deep water sediments, which are often rich in siliceous and car-
bonate material, but lean in clay minerals and iron. Therefore this important
early diagenetic process of carbon consumption and pyrite formation is most
important in shallow marine sediments.
The general equations describing the formation of iron sulfides and the
related consumption of organic matter (after Leventhal 1983; Berner 1984) are:
S042 + 2CH20 ----+ 2HC0 3+H 2 S
6
• II Calc. shale
• II "Low carbon Zone" ..
-
• (2)
~ • I Marlslone
CIJ 4
S
{!. 2
0
0 2 4 6 a 10 12 14
TOC(%)
10
a
-S
~ 6
CIJ
(2)
{!. 4
2
0
0 2 4 6 a 10 12 14 16 1a
TOC (%)
Fig. 5.12. Total sulfur and organic carbon weight percentages of samples from different
lithological units within the Posidonia Shale in northern Germany (above) and reconstruc-
tions of "original" organic carbon values following the bacterial reduction pathway. Regres-
sion lines 1, 2, calculated for the upper plus lower part and the central part of the Posidonia
Shale profile investigated. Carbon loss (17%, 32%) was calculated for samples characterized by
low and high sulfur/organic carbon ratios, respectively. Average organic carbon values of the
"low carbon zone" within the Posidonia Shale and of the upper unit I are 6.7% and 10.8%,
respectively. (Littke et al. 1991 b)
Organic Matter
Carbonate Silicate
Fig. 5.13. Triangular plot of original sediment composition of Posidonia Shale from northern
and southern Germany. Organic carbon percentages are the sum of measured organic carbon
contents and the organic carbon loss due to sulfate reduction (see Fig. 5.12). Open circles,
samples from northern Germany; dark symbols, samples from southern Germany. The ma-
turity corresponds to about 0.5% vitrinite reflectance. (Littke et al. 1991a)
306 R. Littke et al.
lolites and solution seams. Examples for this diagenetic enrichment are de-
scribed for three important petroleum source rocks: the Permian Bone Springs
Formation in Texas (see photos in Littke 1993), Triassic carbonates from Italy
(Leythaeuser et al. 1995), and the Jurassic Lower Smackover Formation (Sassen
et al. 1987) which extends from Texas to Florida. Except for the latter for-
mation, alginites are the predominant macerals in these carbonates. Usually
the same maceral compositions are observed in the carbonate and the inter-
calated solution seams or stylolites. However, these macerals occur finely
disseminated and in low concentrations in the carbonate and in very high
concentrations in the solution seams or stylolites. Based on transmitted light
studies on kerogen concentrates Sassen et al. (1987) showed that the organic
matter of the Lower Smackover carbonates consists mainly of algal-derived
amorphous kerogen. While the average organic carbon content of the
Smackover Formation is only 0.5%, the mean value for the stylolites is 10%,
and the maximum value is 63%.
Due to the limited iron availability in shallow marine carbonate sequences,
sulfur incorporation into the organic matter during early diagenesis is a
common phenomenon. One example is Upper Cretaceous carbonates west of
the Dead Sea. The incorporated organic matter is mainly of algal origin with
some terrigenous contribution and was deposited under reducing conditions
(Spiro et al. 1983). Activity of sulfate-reducing bacteria induced sulfur in-
corporation in the organic matter to a vast extent (up to 12%!; Dinur et al.
1980). Such sulfur-rich kerogen produces a petroleum rich in asphaltenes, i.e.,
an "immature oil," at low levels of thermal maturity (Rullk6tter et al. 1984;
Tannenbaum and Aizenshtat 1985).
In summary, shallow marine source rocks may be rich in oil-prone organic
matter and extend over vast areas. The degree of organic matter degradation is
often less severe than in the case of deep marine source rocks. However, a
significant organic carbon loss due to degradation reactions (sulfate reduction
and organic matter oxidation) affects even those source rocks which were
deposited under anoxic waters. Furthermore, in shallow-marine carbonate
source rocks the distribution of organic matter is often diagenetically altered
by processes such as pressure solution and stylolitization.
5.8
Evaporitic Environments
Kenig et al. (1990) and Kenig and Huc (1990) described organic matter from
modern carbonates deposited in a hypersaline lagoon in Abu Dhabi. The la-
goon provides three principal sources of sedimentary organic matter: micro-
bial mats, mangroves, and seagrass (Fig. 5.14 and Table 5.9). The latter grows
in the central part of the lagoonal area, where Corg values reach 1.3% in surface
sediments. Decreasing Corg values with increasing depth of burial could in-
dicate that preservation of seagrass in the upper centimeters of the sediments is
poor, but other explanations are also possible (Kenig et al. 1990). Mangroves
grow at shallower water depth in the intertidal zone (Fig. 5.14). One mangrove
soil contains 8.2% Corg and consists of root and leaf (cuticle) tissues (Kenig and
Huc 1990) at greater depth of burial, Corg values are lower (0.5-4.6%; Ta-
ble 5.9). Organic matter in the supratidal sabkha environment is derived from
microbial mats. Corresponding sediments consist of interlayered detrital
(storm) deposits and organic mats with Corg values between l.6% (seaward)
and 4.5% (landward; Kenig and Huc 1990). The organic matter of all three
principal sedimentary environments is hydrogen-rich (HI = 400-750 mg hc/g
Corg)'
While Corg rich sediments accumulate in the sabkha and intertidal zone of
the Abu Dhabi lagoon, the adjacent shallow marine carbonates (ooliths) are
poor in organic carbon (0.1%, Kenig et al. 1990). Higher Corg percentages (0.2-
0.4%) and considerable hydrocarbon quantities were reported for ooliths from
the British Jurassic (Ferguson 1987), and much higher Corg values were found
by Ferguson and Ibe (1982; 2.3% Corg ) for recent ooids. At least with respect to
high Corg values in ancient oolithic limestones, it is noted that (part of) the
organic matter may be an oil residue, i.e., oolithes can serve as petroleum
reservoirs (Horsfield et al. 1991).
Barbe et al. (1990) reported on a modern Spanish salina (Fig. 5.15 and
Table 5.9). The carbonates deposited in the pond at relatively low levels of
evaporation contain 3.1-3.4% Corg. Sulfates and halite, precipitated at higher
levels of evaporation, contain much less organic carbon (0.5% and 0.25%,
respectively). This is mainly a dilution effect. Accumulation rates of organic
carbon are high for sulfates and halites because these sediments are deposited
at extremely high sedimentation rates and form the bulk of the total evaporitic
sequence. Barbe et al. (1990) demonstrated that the molecular composition of
=~ :
1/111 Halite
Domain
•
70-140 gil >290 gil
: 140-220 gil :
Diatom..
GreenA!gae Sulphur Photolrophlc Baderla
Artemla Salina
DunaJle!la
HaIobac:!erIa
Fig. 5.15. Schematic section through a modern saline in Spain with evaporation ratios, salt
concentrations and occurrence of different groups of biota. (Barbe et al. 1990). (Reprinted
from Barbe et al., Characterization of model evaporitic environments through the study of
lipid components, 1990, pp 815-828, with kind permission from Elsevier Science Ltd, The
Boulevard, Langford Lane, Kidlington OX5 1GB, UK)
Deposition of Petroleum Source Rocks 309
0
40
0
o NOrdlinger Ries
~ 0 o Messel
30
DO t; Wenzen
0 0 Mulhouse Basin, S-Bed
~ o 0
0
0 • Marls
2' 20 .. Anhydrites
0
() 0
JBO
0
o 0
10
0 o
80 cPg o
• •••
0
00 0 0 •
0
50
•
100 150 200 250 300 350
Fig. 5.16. Organic carbon percentages (C org ) versus solvent extract yields of samples from an
evaporitic environment (Mulhouse basin, S-bed; Hofmann 1992) in comparison to other
immature oil shales. (Littke et al. 1988)
310 R. Littke et al.
of the evaporites in the Mulhouse Basin were published in 1993 and mainly
molecular geochemical aspects of the organic matter in several evaporitic se-
quences were presented in 1995, both in a special volume of Organic Geo-
chemistry.
In summary, in evaporitic sequences high organic matter concentrations
can be expected only in carbonates and anhydrites, as well as in intercalated
shales. In halites (and potassium salts), Corg values are low due to the dilution
of organic matter by rapid precipitation of minerals. Organic matter in evap-
oritic sequences is often hydrogen rich; this may be due to an inhibited de-
gradation before and after deposition. Geochemical differences between var-
ious evaporitic settings are more obvious than similarities. Even relatively well-
established organic indicators of highly saline depositional environments such
as low pristane/phytane ratios (ten Haven et al. 1988), predominance of even
numbered over odd numbered n-alkanes (Welte and Waples 1973), and the
occurrence of gammacerane (Mello et al. 1988) do not seem to be of general
validity (de Leeuw and Sinninghe Damste 1990).
5.9
Lakes
Lakes are known to be suitable settings for deposition of rich petroleum source
rocks. According to the kerogen classification scheme of Espitalie et al. (1977),
the most hydrogen-rich type I kerogens (H/C approx. 1.5 or more, O/C lower
than 0.1) are derived mainly from lacustrine depositional environments (Tissot
and Welte 1984).
The organic richness of lake deposits is extremely variable and depends
upon the nutrient supply by inflowing rivers, water circulation in the lake, and
the stability of water stratification. A mapping of organic richness based on
organic carbon measurements on recent sediments from Lake Tanganyika was
presented by Huc (1988a,b). His results demonstrated that - similar to the
situation in silled marine basins such as the Black Sea - the most organic
matter-rich sediments were deposited in the deepest part of the lake. The
distribution pattern is, however, complex and testifies to the fact that not only
water depth affects organic richness.
With respect to the depositional controls on the characteristics of organic
matter in lacustrine oil shales, a detailed comparative study was undertaken by
Horsfield et al. (1994) on two members of the Eocene Green River Shale from
the southwestern United States. The Laney Shale and the Luman Tongue
member were deposited under vastly different environmental conditions (open
versus closed lake, humid versus arid climate, freshwater versus alkaline lake)
and these environmental conditions greatly affected the chemical character-
istics of the organic matter. For example, hydrogen richness and hydrocarbon
generation potential as well as the amount of terrigenous organic matter differ
greatly between the two members. Only the sediments from the alkaline lake
stage contain predominantly algal-derived kerogen (alginite) and yield much
hydrocarbons upon pyrolysis. The freshwater lake stage, however, produced
Deposition of Petroleum Source Rocks 311
Table 5.10. Organic matter characteristics of deposits from an Eocene freshwater lake (Messel)
and a Miocene hypersalinar lake (Niirdlinger Ries)
~ssel, Finely laminated, 28.3±6.1 {7-40)a 1.0±0.6 min (0.2-2.4) 553±43 {470-640)a
W Germany fine-grained shales
locene)
rdlinger Ries, Extremely variable 6.9±5.3 {1.6-25)C 2.4±1.2 min (0.5-4.8) 513±176 (l77-920/
mthern Germany finely laminated
.1iocene) shales, marls tones,
dolomites and
others b
sediments. Also, great differences between Corg values in marginal and central
parts of the basin were recognized (Rullkotter et al. 1990).
The type of organic matter deposited in the two lakes is also different and
clearly depends on the environmental conditions in the adjacent land areas. In
the case of the Messel Shale remains of higher land plants were fluvially
transported into the lake. Accordingly, the Messel Shale kerogen is composed
of about 20% terrigenous higher plant material and 80% autochthonous ma-
terial derived from subaquatic organisms (Jankowski and Littke 1986; Rullk-
otter et al. 1988). In the Nordlinger Ries Shale, terrigenous organic particles
such as vitrinite and inertinite are generally less abundant, especially in the
central part of the deposit (Rullkotter et al. 1990). This is probably due to the
lack of an effective transport mechanism, i.e., the Ries was a closed lake in
contrast to the open lake Messel. Therefore terrigenous particles were mainly
deposited at the rims of the basin.
Another important environmental factor influencing kerogen composition
is water chemistry. The Ries lake had variable, often anomalously high sali-
nities (Jankowski 1981). Organic matter input into the sediments changed with
changes in salinity, leading to substantial variability in organic petrographic
and bulk geochemical characteristics, for example, in HI values (Table 5.10).
The fact that the three most hydrogen-rich samples of the Nordlinger Ries
Shale (HI greater than 800 mg hc/g Corg ) are characterized by a fluorescing,
structureless organic groundmass (Rullkotter et al. 1990) may indicate an
origin from bluegreen algae, which are relatively resistant to hypersaline
conditions (Jankowski 1981: 135; Barbe et al. 1990). No salinity changes af-
fected the Messel Shale, which contains a remarkably homogeneous kerogen on
a petrological and bulk geochemical basis. Its rather uniform, intermediate HI
values (Table 5.10), normally indicating type II kerogen, are the effect of a
mixture of aqueous (type I) and terrigenous (type III) organic matter.
Also, ionic composition of the water in the two lakes was very different.
Lake Messel was rich in iron, whereas the Ries lake, completely surrounded by
Malmian carbonates, was dominated by alkaline and alkaline earth ions (Na, K,
Ca, Mg) and poor in iron (Jankowski 1981). This difference in iron availability
greatly affected the sulfur content of the organic matter. In the Messellake little
sulfate was available, and sulfur was mainly fixed in pyrite. In the Ries lake
more sulfate was available, and fixation of sulfur in pyrite was inhibited due to
the low iron concentration. A great part of the available sulfur was therefore
bound in organic matter, leading to anomalously high atomic Sorg/Corg ratios
(up to 0.08, Rullkotter et al. 1990). The Nordlinger Ries data show that hy-
persaline lakes may produce sediments as rich in sulfur as marine sediments
(Fig. 5.17). In this case the sulfur versus Corg plot cannot be used to differ-
entiate between marine and lacustrine sediments (Berner 1984).
In the Nordlinger Ries deposits extract yields are much higher than would
be expected for immature organic matter at very shallow depth (Fig. 5.16). In
most samples, phytane is the most abundant single aliphatic compound and
phytane/pristane ratios are extremely high (greater than 10) as typical of se-
diments deposited under hypersaline conditions (ten Haven et al. 1988). The
"aromatic hydrocarbon" fraction is dominated by thiophenes, thiolanes, and
Deposition of Petroleum Source Rocks 313
10,---------------------------------------.
2
+
+ 00
++1-
00 +
• •
0 q,
')too o
•
0
0
• •'"• • • ••
0
+ 0
• •
0 10 20 30 40
Corg (0/0)
Fig. 5.17. Organic carbon percentages (C org ) versus sulfur percentages for three different,
immature oil shales. Crosses, Lower Toarcian Posidonia Shale from the Wen zen borehole;
circles, hypersaline, lacustrine Nordlinger Ries deposit of Miocene age; stars, Eocene, lacus-
trine Messel Shale
5.10
Fluviodeltaic Coal-Bearing Sequences
Fluvial and deltaic sediments are among the most important source rocks for
natural gas (e.g., Lutz et al. 1975; Masters 1984; Rice et al. 1989; Littke et al.
1995; Lopatin et al. 1995) but are also reported as source rocks for oil, espe-
cially in the Australo-Indonesian realm (Thomas 1982; Thompson et al. 1985;
Durand and Paratte 1983; Risk and Rhodes 1985; Shanmugam 1985; Khavari-
Khorasani 1987; Horsfield et al. 1988; Hvoslef et al. 1988). Fluvial and deltaic
sequences are highly variable with respect to concentration of organic matter.
314 R. Littke et al.
This heterogeneity is partly due to the fact that preservation of organic matter
is strongly affected by differences in climate and exposure to either subaerial or
subaquatic conditions after deposition. In fluvial and deltaic sequences the
bulk of the organic matter consists of parts of higher land plants, most of
which are deposited close to but not exactly at the place of plant growth
(Scheihing and Pfefferkorn 1984). As growth of higher plants is inhibited in
arid regions, deposition of organic matter-rich fluvial and deltaic sediments is
usually restricted to humid climates. Furthermore, source rocks are not ex-
pected to occur in pre-Devonian fluviodeltaic rocks because the evolution of
higher land plants only started during the late Silurian.
Coal-bearing fluvial and deltaic sequences deposited in humid climates
contain the highest concentration of organic matter in rocks both on a meter
scale (50-99% Corg in coals) and on a basin-wide (kilometer) scale. Figure 5.18
compares organic matter percentages for five coal-bearing basins according to
a compilation by Scheidt and Littke (1989). In most of these basins more
organic matter is fixed in coals than finely dispersed in clastic sediments. The
average amount of total organic matter ranges from 4 to 12 vol%, and the ratio
of coal to dispersed organic matter from 0.7 to 2.5% over intervals of several
hundred to more than a thousand meters thickness.
Total amounts of dispersed organic matter are different in different lithol-
ogies, as exemplified for the Ruhr basin in Figure 5.19 (Scheidt and Littke
1989). For this area a decrease in organic matter content with increasing grain
size was found, for example, mudstones on an average contain more organic
matter than siltstones and sandstones. More than 2 vol% dispersed organic
matter on an average is fixed in gray mudstones, one of the major lithologies.
In contrast, the various siltstone and sandstone facies contain less than 2 vol%
and often only 1 vol% dispersed organic matter. The only exception are rare
conglomeratic sandstones with more than 2 vol% dispersed organic matter in
the form of coal pebbles and barks of twigs and stems. Baker (1962) and Huc et
al. (1986) reported similar values for shale samples from other coal-bearing
sequences, i.e., the Cretaceous Douala basin (1-3% Corg), the Miocene Maha-
kam delta (1-4% Corg ), the Westphalian in the Paris basin (1-5% Corg ), and the
Upper Carboniferous of the Cherokee group of Kansas and Oklahoma, United
States (1-5% Corg in gray shales). Few clastic rocks in coal-bearing basins
contain more than 10% Corg. Exceptions seem to be black shales (see Fig. 5.19)
derived from marine incursions (Wenger and Baker 1986: up to 20% Corg ) and
mudstone partings within coal seams (Littke and ten Haven; 1989: up to 32%
Corg ). As discussed above, the organic richness of the former group is ex-
plained by high algal production and the occurrence of humic precipitates
fostered by the flooding of swamps, whereas the richness of the latter is partly
due to the in situ growth and preservation of roots after clastic deposition
(Scheidt 1988).
In fluvial and deltaic sequences, terrigenous organic matter usually pre-
dominates over aquatic organic matter (e.g., Scheihing and Pfefferkorn 1984;
Scheidt and Littke 1989; Smyth 1989), although the latter occurs in interbedded
(1) transgressive marine deposits (e.g., Wenger and Baker 1986) and (2) la-
custrine deposits such as rare sapropelic coals (e.g., Stach et al. 1982). Terri-
Deposition of Petroleum Source Rocks 315
Eromongo Bosin Ellmouth Pfateou Soo,.- Ateo Oonez- Bosin Ruhr - Areo
Jvrossk Triossic CC/boniferous Corboniferous Carboniferous
Fig. 5.18. Volume percentages of organic matter bound as coals seams and as dispersed
organic matter in different coal-bearing basins. (Compilation by Scheidt and Littke 1989,
based on literature data).
genous organic matter is known to contain less hydrogen and more oxygen
than aquatic organic matter (Pelet 1983; Tissot and Welte 1984). Accordingly,
in immature fluvial and deltaic rocks, H/C ratios of kerogen are generally lower
than 1 and OIC ratios greater than 0.2 (Boudou et al. 1984; Huc et al. 1986).
Hydrogen Index values of coals are generally in the range of 150-300 mg hcl
g Corg at immature or marginally mature stages (Table 5.11); similar values are
typical for handpicked vitrinites from coals (Littke et al. 1989) and suggest an
intermediate hydrocarbon generation potential. Interestingly, HI values of
kerogen in mudstones and siltstones interbedded with the coals are generally
lower (Table 5.11), although the petrographic composition of the organic
matter is roughly similar (Scheidt and Littke 1989). This difference is tenta-
tively explained by an inhibited expulsion of high molecular weight hydro-
carbons generated from the coals. The resultant low expulsion efficiency causes
316 R. Littke et al.
siltstones
"OJ..c
·e ~
.. "1ii.. "1ii..
c
".. ..
.!l .!l
.,0 c " u
i
...
c
%
4
dispersed organic
o
mean- 3.0 u
%
30 ~--------4-------------~------------------~
frequency of rock
25
20
15
10
Fig. 5.19. Volume percentages of organic matter in different clastic rocks of the Carboniferous
Ruhr basin (above) and percentage of these rock types in this sedimentary sequence (below).
The grain size of the sediments as well as the average grain size of the organic clasts increases
from left to right. The volume percentage of organic matter in black shales (about 30%) is
offscale. (Scheidt and Littke 1989)
Deposition of Petroleum Source Rocks 317
Table 5.11. Organic matter characteristics of coal-bearing strata (coals, mudstones, siltstones).
(Horsfield et al. 1988; Ramanampisua et al. 1990; Littke et al. 1989)
Rr> Mean vitrinite reflectance; HI, hydrogen index, mean (maximum in parentheses); V,
vitrinite; I, inertinite; L, liptinite.
Vitrinite ~ U~
Q
~ ~
• Ardjuna basin (Tertiary)
o • Eromanga basin (Jurassic)
'V l' Morondava basin (Permian)
60%
90%
Fig. 5.20. Average vitrinite, inertinite, and liptinite percentages of coals and corresponding
kerogen in clastic rocks in different coal-bearing basins. DOM, dispersed organic matter
5.11
Source Rocks and Tectonics of Petroleum Basins
The relationship between source bed occurrence and basin tectonics is difficult
to ascertain. This limitation results from several related deficiencies. Often the
unequivocal identity, such as through geochemical characterization or corre-
lation with accumulated hydrocarbons, of the source rock is unavailable.
Further, although a petroleum basin may be classifiable on a tectonic basis
(often based on a present-time view), these tectonic conditions may differ from
the tectonic framework which existed during the time pertinent to source rock
deposition. As noted by Klemme (l980, p. 261), "crustal mobility produces
Deposition of Petroleum Source Rocks 319
Typed ~
Interior Simple Cratonic Basins Cratonic Sag Basins
~ li '8~ I
:'=fIl
.~ Type 2 o .Is
0
IS '8 Composite
a) large, b) small, 2a Complex
! :go bO
U:::?J
G) Cratonic Foredeep
5] Foreland Basins
~ ~
"0
J 5 '60 i:!
Type 3 i:2 .= ~<U
B IS Rifted Grabens Rifts and Grabens
- Rift &1.~ i5~
Type 4 (in part) (in part)
Downwarp into Small Atlantic-type Foreland
I--- ? ? ?
Ocean Basin: a) closed, Fordedeep Divergent Margin
b) trough only, c) open (Episutural Basins) Back-arc
I a
~ Type 5 .J
G) "0 = Atlantic-type Passive ~<U Divergent Margin
.~ Pull-Apart '60 ~ IS Margins (transverse)
a) parallel, b) traverse ~.~ ~~
IS ~ i:2 J
0;:: Type 6
~ ForeArc Fore-arc
Subduction .g ij
&1 ] Back-deep and Marginal e!l<'l Back-arc
~ ~ a) fore-arc, b) back-arc,
a::I ::I California-type Strike-slip
~ c) non-arc ~~
Type 7
'" ~
& fIl Pannonian-type 8
~ Median ?::I
t"'"
TypeS
Deltas and Fans
~ Deltas ~
n>
~
5.12
Conclusions
Table 5.12. Basin types and selected petroleum related characteristics. (Compiled with minor modification from Klemme 1980)
Basin type 1: Interior 2: Composite 3: Rift 4: Downwarp 5: Pull-apart 6: Subduction 7: Median 8: Delta
simple (closed-open)
ganic material greatly determines the quality of the petroleum. For example,
sulfur-rich kerogen which is typical for iron-depleted source rocks produces
sulfur-rich oil, and coaly organic matter tends to generate more gas (higher
gas/oil ratios) than algal-derived kerogen. However, not only the type of oil or
gas produced but also the total mass and volume are greatly governed by
source rock characteristics. Masses and volumes greatly depend on the
thickness of the source rocks, chemical nature of the organic matter, total
amount of organic matter, areal extent, and expulsion characteristics and
drainage volume. Therefore information on the distribution, thickness, and
facies variation of source rocks in sedimentary basins is highly desirable. This
information is also necessary in any numerical basin modeling, where it is used
in combination with the burial and temperature history and kinetic data to
calculate the petroleum generation history in sedimentary basins.
Depositional environments of petroleum source rocks have commonly been
categorized as either "nonmarine" or "marine." Considering the broad variety
of depositional settings and conditions, such a classification is too simple to
provide adequate insight into source rock deposition. As an alternative we have
attempted to treat source rocks in a framework similar to the depositional
categories as currently discussed by sedimentologists and stratigraphers.
The depositional settings for source rocks greatly affect the source rock
properties. For example, source rocks deposited in anoxic lakes or anoxic
shallow marine basins tend to contain a very hydrogen-rich kerogen derived
from plankton (type I or II; Table 5.13), whereas those deposited in fluvial,
deltaic, and deep-marine basins tend to contain predominantly hydrogen-lean
kerogen (type III) derived from higher land plants. Undoubtedly, marine
source rocks provided most giant oil fields of the world (such as those of the
Arabian peninsula; Table 5.13). Some of these oil shales are of great lateral
extent, such as the Posidonia Shale or the Kimmeridge Clay in northern and
central Europe.
Commercial oil fields also result from source rocks deposited in lakes and
the largest oil field related to such lacustrine source rocks is probably the
Daqing field in the Songliao basin of China (Kulke 1994). Other examples exist
along the coasts of western Africa and Brazil, where hydrogen-rich, alginitic
kerogen is present in Lower Cretaceous deposits which witness the early rifting
of the Atlantic Ocean.
The most giant gas accumulations in the world occur in northwestern Si-
beria and originate from coaly (type III) source rocks situated at shallow depth
(Lopatin et al. 1995; Table 5.13). The large gas fields of the eastern Netherlands
and northern Germany are also derived from coaly organic matter, but these
source rock sequences are situated at great depth. In addition to methane, the
coals also generated significant amounts of molecular nitrogen gas in this area
(Littke et al. 1995).
The concentration of organic matter both in progradational submarine fans
and in evaporitic environments is often smaller than in the above discussed
settings whereas the quality with respect to hydrocarbon generation may be
good or at least moderate. Evaporitic sequences such as the Sta6furth-Kar-
bonat of the Late Permian Zechstein formation in Germany can act as effective
324 R. Littke et al.
Table 5.13. Characteristic features of different settings for petroleum source rock deposition
+++, Extremely important; ++, very important: +, important especially for gas generation; 0,
less important or unknown; **, extensive to very extensive; *, small to extensive.
source rocks for petroleum. One advantage of this type of source rock is the
intimate connection with rather impermeable salt cap rocks.
However, many exceptions exist for the general pattern summarized in
Table S.l3. For example, coaly organic matter is regarded as the source of some
important oil (rather than gas) accumulations (e.g., Gippsland basin, Aus-
tralia). The many factors controlling petroleum generation and expulsion from
source rocks are the principal reason why any classification of source rocks
remains unsatisfactory. Therefore source rocks must be specifically mapped
and studied for each individual basin and petroleum play. The results of these
specific investigations are necessary ingredients of any sophisticated petroleum
exploration and basin modeling.
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Chapter 6
The Bulk Composition of First-Formed Petroleum in
Source Rocks
Chapter 6: Overview and Insights
6.1
Introduction
lInstitut fiir Erdal und Organische Geochemie (ICG-4), Forschungszentrum Jiilich GmbH,
52425 Jiilich, Germany
tJ)
Q) 80
Q..
~
tr...
co
:l
(.) 60
Q)
-
0 ~UI nes
( opara' ins)
::2!:
0
40
-
Q)
C)
co
c:
Q)
(.)
tr... 20
Q)
0..
o
Gasoli ne
C,-C"
Kerosine
C"-C,,
I
40
Diesel
fue l
C,,-C..
Heavy
gas oil
C..-C,
Lubricating
oil
C",-C..
80
Res iduum
>C..
100
I
Crude Oil (Vol. %)
Fig. 6.1. Chemical composition of a crude oil in terms of molecular type. (Hunt 1979). From:
PETROLEUM GEOCHEMISTRY AND GEOLOGY by Hunt. Copyright © by W. H. Freeman
and Company. Used with permission.
Until the middle 1980s and early 1990s, predicting the occurrence of gas
versus crude oil using organic geochemistry relied only minimally on the ac-
tual composition of petroleum. For exploration purposes, especially in virgin
territory, crude oil was considered mainly as a single entity and gas as another,
and the presence of one or the other was predicted using an overriding em-
phasis on measured or anticipated source rock quality and maturity. These
concepts, established 30 years ago and more (Forsman and Hunt 1958; Philippi
1965; Landes 1967; McIver 1967; Tissot et al. 1974), were that hydrogen-rich
kerogen disproportionates when mature to form liquid-rich, gas-poor petro-
The Bulk Composition of First-Formed Petroleum in Source Rocks 339
2. The second observation is that the occurrence of gas versus oil in petro-
leum reservoirs is strongly dependent on secondary migration phenomena,
and that source rock influences can be vastly overshadowed. This is based on
the application of reservoir engineering principles to carrier-reservoir systems
(Schowalter 1979; Heum et al. 1986; England et al. 1987; England and Mack-
enzie 1989). Petroleum density and viscosity are controlled directly by the
relative proportions of low-density, low-viscosity consitituents in the C1-C4
range, on the one hand, and high density, high viscosity constituents, especially
colloidal components such as asphaltenes, on the other. Thus a fall in confining
pressure below the bubble point pressure during secondary migration leads to
the progressive exsolution of free gas from the petroleum (Fig. 6.2), and a rapid
increase in viscosity and shrinkage of the remaining liquid phase with con-
tinuing pressure decline (Neumann et al. 1981). High-GOR petroleums gen-
erally begin to exsolve a separate gas phase at higher pressures and
temperatures than do low-GOR petroleums. Density is also controlled by the
gas-oil ratio and the relative abundances of hydrocarbons and non-hydro-
carbons in the C1S + fraction (Hunt 1979; Connan and Coustau 1987). Ad-
ditionally, the absolute value of viscosity for the liquid phase, and hence Darcy
flow behaviour, is dependent on its composition with asphaltic crude oils
generally being more viscous than low-wax paraffinic oils, for example (Neu-
mann et al. 1981). Because viscosity increases with the molar mass for n-alkane
homologues, high-wax paraffinic petroleum is more viscous than the low-wax
paraffinic type. However, this relationship is not always straightforward
(Hernandez et al. 1983) because the physical interactions of monomolecular
and macromolecular components in highly complex mixtures are not well
understood (Mitchell and Speight 1973). It is consequent that the quantitative
determination of bulk composition for petroleums first-formed in source rocks
is a requirement for modelling the migration of petroleum charges from source
rock kitchens to traps using a petroleum engineering approach. This is illus-
trated in Fig. 6.2 by the example of hypothetical petroleum charges with dif-
fering original GORs which migrate from a depth of 4500 m to a trap at
2000 m. Using the Prospect Analyzer computer program, with input of the
petroleum properties published by England et al. (1987), the temperature
profile from Dahl and Augustson (1993) and an average pressure gradient
13 mpa/km, it can be seen that the absolute volumes of gas-saturated oil and
oil-saturated gas at the prospect are highly dependent on the original petro-
leum composition.
3. Related to the above is the finding by Thompson (1988), supported by
Dzou and Hughes (1993), that petroleums in any given region can be con-
sidered to have one original composition, but that this is strongly modified as a
result of evaporative fractionation during reservoir leakage. Original oils ex-
hibit varying degrees of light end loss, whereas the lost material form mi-
gratory gas/condensates, some of which can accumulate in shallower traps. The
losses are accompanied by fractionation so that the remaining residual oils
show changes in the intermolecular ratios termed aromaticity, normality and
paraffinicity, their extent being proportional to the degree of light end loss.
Further modifications can occur within petroleum accumulations during in-
The Bulk Composition of First-Formed Petroleum in Source Rocks 341
0 1000 2000 3000 0 1000 2000 3000 0 1000 2000 3000 0 1000 2000 3000
0 I I I I
1000
/'-
2000
E
z:
Q.
Q)
"U
3000
•
4000
5000
---+-gas
oil Gas Oil
1
Fig. 6.2. Changes in the volumes of gas and oil phases as they migrate from 4500 m to
shallower depths. Scenarios for different starting GORs are shown
version when gas cap expansion displaces oil out of the trap, by preferential
leakage oflight components through seals, or via microbial biodegradation and
water washing (Bailey et al. 1974; Krooss et al. 1992). Knowing the composition
of the initially reservoired petroleum is required in order to recognise the full
extent of evaporative fractionation (Thompson, personal communication) and
then to infer migration pathways and predict the existence of shallower sec-
ondary targets.
The first step in unravelling all types of fractionation phenomena is to
determine the bulk composition of the petroleum that is first-formed in the
342 B. Horsfield
source rock because all subsequent processes simply act upon and modify this
original composition. There are two basic ways of doing this: by the analysis of
rock and oil samples from selected geological study areas and by laboratory
experiment. Cuttings gas and extractable hydrocarbon data from source rocks
at different maturity levels may give some clues as to the in situ composition of
the generated petroleum but sampling and migration losses are regarded as
being high, making absolute quantitation difficult (Price 1989). Additionally
absolute gas-oil ratios of generated and expelled petroleums are not actually
known with any certainly because of the impracticality of sampling deep (ca.
5-8 km) source rock kitchens and in view of the difficulty in distinguishing the
respective influences of co-occurring generation and expulsion. It is therefore
left mainly to indirect methods such as the laboratory pyrolysis of kerogen,
with their high precision but inherent uncertainties as to direct geological
applicability, to infer gas versus oil generating potential or define likely
compositional attributes of petroleums in source rock kitchens. This chapter
reviews both approaches, but concentrates on laboratory experiments which
have proved more valuable in recent years.
6.2
The Direct Analysis of First-Formed Petroleum
,....2
E
C Oll+Gas
..c:
a.
Q)
Cl
3
Oil Gas
4
0,02 0,2 2 20 200
GOR (kg/kg)
Fig. 6.3. Surface gas-oil ratios of oils and gases from offshore Norway as a function of depth.
Open circles, oil accumulation; closed circles, gas accumulation; horizontal lines connect co-
existing gas caps and their underlying oil leg. (After England and Mackenzie 1989)
immature through early mature Bakken Shale (Williston Basin, USA) con-
tained both light and heavy aliphatic, alicyclic and aromatic hydrocarbons,
whose gas-oil ratio was 0.18 kg/kg, again confirming the above results. Ad-
ditionally, a strong positive correlation with TOC attested to the indigenous
nature of the gas (Fig. 6.4). Interestingly, average gas yields were on the order
Fig. 6.4. Relationship between organic richness (TOe) and gas yield (from thermovaporisa-
tion) for the Bakken Shale. (Muscio et al. 1994). (Reprinted from Muscio et aI., Occurrence of
thermogenic gas in the immature zone - implications from the Bakken in-source reservoir
system, 1994, pp 461-476, with kind permission from Elsevier Science Ltd, The Boulevard,
Langford Lane, Kidlington OXS 1GB, UK)
The Bulk Composition of First-Formed Petroleum in Source Rocks 345
of 6 mg/g TOC, which should amount to about 20% of the the total gas gen-
erating capacity according to pyrolysis-GC. The result signified not only that a
high proportion of the kerogen's total gas-generating potential had been rea-
lised early during maturation, but also that the generated gas had been retained
in the rock during recovery. The correlation with TOC indicated that the gas
was adsorbed on or absorbed within the kerogen, whose open structure partly
consists of aromatic or readily aromatisable moieties. Absorption is feasible
according to the results of Young and McIver (1977) who showed that light
hydrocarbon retention is directly related to the presence of solid organic
matter. The higher GOR values noted for higher maturity levels by Cornford
(1993) could not be corroborated in the case of the Bakken Shale because of
losses resulting from migration or during sample recovery, possibly in part due
to changes in kerogen structure and hence absorptive capacity with increasing
maturation (Fig. 6.4).
High Cl-C lO contents were detected in the thermovaporisation products of
the alginitic Alum Shale of Scandinavia over a wide range of H/C ratios
(Horsfield et al. 1992), and gas-oil ratios fell in the range 0.3-0.6 kg/kg. Sim-
ulated maturation experiments verified that gases were amongst the main
generation products. A common denominator with the Bakken Shale is that
this kerogen has a high proportion of thermally labile aromatic and/or alicyclic
groups. Difficult to reconcile are unpublished light hydrocarbon data (head-
space and cuttings gas) and solvent extract yields (C 1S + range) for early mature
(Ro=0.55-0.70%) Jurassic-Cretaceous source rocks from two wells on the
northern slope of Alaska (Fig. 6.5). High values of gas-oil ratio, approximated
by C1 -C 4 and C1S + concentrations and represented by two trends (20 and
46 kg/kg), were stratigraphically distinct in both wells, and possibly related to
organic matter type or petrophysical properties. The observed correlation of
gas and C1S + extract yields appears to rule out gas contamination ("trip gas")
from the mudstream. The range of values is actually more typical of condensate
dissolved in gas than gas dissolved in oil, according to the results of England
and Mackenzie (1989) summarised in Fig. 6.3. It is not known whether this
composition truly represents an early generation product (see Muscio et al.
1994), or whether the high-GOR components seen in the rock represent the oil-
saturated gaseous residuum after preferential expulsion of a low-GOR liquid
phase (see Fig. 6.3). Nevertheless, the example serves to illustrate that yields of
volatile hydrocarbons may provide a source of important information for
studying geochemical processes.
The results discussed above point to a substantial proportion of a kerogen's
total gas generating potential being realised early on in catagenesis, but in
amounts that are usually subordinate to those of heavier components. Gas-oil
ratios are therefore generally low, falling in the range 0.2-0.3 kg/kg, and
possibly as low as 0.1 kg/kg or less, though in this case material losses can be
suspected too. It is not known how common it is to find occurrences of first-
formed petroleums with higher gas-oil ratios, but they undoubtedly exist, not
only at high levels of thermal maturation but also at low levels of thermal
stress. The roles played by kerogen type - and this revolves around the re-
sponse of its molecular composition to increasing thermal stress - have yet to
346 B. Horsfield
80000
•
70000
•
•
-
60000
-
./.
•
Q.
•
Q.
50000
tn
- •
C)
C
:;::
::::s 40000
0
o
'C
C
CO 0/ o
o •
G)
() 30000
CO
Q. • <Do
tn
'C gp.
o i
~
CO
G) 20000 • o
0
C
.
• 10000
c5
O~-----.------r-----.------r-----'------;
o 200 400 600 800 1000 1200
6.3
Kerogen Composition
6.3.1
The Typing of Kerogens by Elemental Composition
Noble 1994}. Choosing both kerogen quality parameters and kinetic param-
eters is therefore problematical where phase and volume and kinetic modelling
must be performed without direct access to calibration samples. For this rea-
son a classification of organic matter based on not only genetic potential but
also maturation characteristics and kerogen quality is highly desirable for
geochemical modelling {Horsfield 1989}. Both these additional attributes can
be determined by molecular typing using pyrolysis methods. Furthermore,
because molecular similarities exist between genetically related asphaltenes,
heterocompounds and kerogens {Behar and Pelet 1985; Solli and Leplat 1986;
Muscio et al. 1991}, molecular kerogen typing criteria can be extended to the
macromolecular fractions of crude oils and rock bitumen. In this way reservoir
and source facies could be classified using a single frame of reference for
applications in basin modelling {Horsfield et al. 1993a}.
The use of molecular typing can be illustrated using the example of the
Ardjuna Basin in Indonesia {see Gordon 1985; Horsfield et al. 1988; Noble et al.
1991 for details}. The Ardjuna Basin is a major petroleum province in north-
western Java, Indonesia. Non-marine crude oil is produced from Oligocene
through Middle Miocene clastic and carbonate reservoirs. Although a great
variety of compositions are attributable to alteration phenomena such as
evaporation-fractionation and biodegradation, primary petroleums are of the
high-wax type. Based on geological and geochemical considerations the pri-
mary source of all petroleum discovered to date in the basin is the deltaic
member of the Oligocene Talang Akar Formation. Within the Talang Akar
Formation there are three fine-grained lithofacies, these being lower delta plain
coals and interdistributory bay black shales each containing kerogen types II
through III, and delta plain grey shales whose kerogen has a type III compo-
sition. On the logical premise that the immature source of the high-wax oils
must contain long-chain n-alkyl structures, the grey shale lithofacies could be
ruled out as a potential source as these substituents were absent from kerogen
concentrates. These components were present in the pyrolysates of the other
two lithofacies, pointing to high-wax oil-generating potential. There was,
however, no relationship between the abundance of n-alkyl substituents and
kerogen type assignment (II or III). Indeed, within the coal source facies the
best correlation found was that with the proportion of matrix liptinite
(Fig. 6.6A). The hydrogen index was correlated with the contributions of
amber and microscopic resinite particles rather than being equatable with
generative yields of n-alkane precursors (Fig. 6.6B). In other words, good high-
wax oil-generating potential did not coincide with high hydrogen index values
at any given maturity level. Instead, elemental composition was being over-
whelmingly influenced by resin-related macerals whose maturation products
are known to contribute to petroleums {Grantham et al. 1983; Alexander et al.
1987; van Aarssen et al. 1992}, but whose fate in quantitative terms is poorly
understood and is certainly subordinate in this particular case. The assertion
from marine source rock studies that Hydrogen Index is a measure of oil
generating potential (Tissot et al. 1974) cannot therefore be automatically
extended to non-marine source sequences because resinite is a commonly
occurring maceral in Tertiary fluviodeltaic systems.
The Bulk Composition of First-Formed Petroleum in Source Rocks 349
;e 500
~ 50-.------------,---.
~
II)
H'Ig h V0Iale
t'l .7 4
.5;',' ~
•• • •
~ Bituminous Rank .- 400
~ 40 •.54 ~~~ ...", .71
~ 1-_,-------.,..-
• .49
xw
c
:'•
+ .52 z 300-
"'
u30 zw
12 ... --r~i;6
•
Brown Coal
~ f::,' .31 .34 . - Lignite Rank
Cl
0
a: 200-
i= 20 c
:::I >-
III
1:
...a: 100-
~ 10
U
O·~---.---.---.---.---,--~
o 1'0 2'0 3'0 4'0 ~O 60
RESINITE PLUS FLUORESCING VITRINITE (%)
MATRIX LlPTINITE (%)
Fig. 6.6A,B. Organic petrographic and pyrolysis data for Talang Akar coals (Horsfield et al.
1988). A Relative abundance of the coal maceral matrix liptinite versus relative abundance of
n-alkyl moieties in Cs+ pyrolysates. B Relative abundance of resin-derived coal macerals
versus hydrogen index and isotopic composition. (Reprinted from Horsfield et aI., De-
termining the petroleum-generating potential of coal using organic geochemistry and organic
petrology, 1988, pp 121-l31, with kind permission from Elsevier Science Ltd, The Boulevard,
Langford Lane, Kidlington OXS 1GB, UK)
6.3.2
Kerogen Composition and Structure - A Brief Overview
Selective Preservation
CO2 • H20
METABOLITES
MlNERAUSATION
MINERAUSATION
BIOTRANSFORMATION
BIOTRANSFORMATION
BIOMACRO-
MOLECULES
'.
...... ?
\~,
"ClA'~ICAl
PATHWAY"
PRESERVATION
INCORPORATED
lMW BIOMOLECULES " NATURAL
r------....
VULCANISATION"
RESISTANT
BIOMACRO- RESISTANT
LIPIDS
MOLECULES
SULPHUR-RICH
MACROMOLECULES
THERMAL THERMAL
•
DISSOCIATION DISSOCIATION
AND AND
DISPROPORTIONATION DISPROPORTIONATION
Fig. 6.7. The two paths for kerogen formation: selective preservation and neo-condensation.
(Reprinted from Rullkotter and Michaelis, The structure of kerogen and related materials. A
review of recent progress and future trends, 1990, pp 829-852, with kind permission from
Elsevier Science Ltd, The Boulevard, Langford Lane, Kidlington OXS 1GB, UK)
Neo-Condensation
Highly
organized
biopolymers
Individual
monomers
Heterogeneous Increasing
random condensation
and
geopolymers In solubilization
6.4
Choice of Pyrolysis
3a
Fig. 6.8. Conceptual models of kerogen structure (after Behar and Vandenbroucke 1987). la,
2a, 3a, the structures of selected type I, II and III kerogens at the immature stage
354 B. Horsfield
6.4.1
The Concept of Structural Moieties
6
7
Boghead Coal
8
a a 9
10 15 25
20 30
10
Posidonia Shale
IBc a
o
c.
5
=
a:
a
a
p p
Vitrinite
a p
Retention Time •
Fig. 6.9. Open-system pyrolysis-gas chromatograms of three immature kerogens - Boghead
Coal, Posidonia Shale and Vitrinite - reveal the major resolved components seen in geological
samples. n-Alkene/-ane doublets extending to variable chain lengths (numbered), isoprenoid
alkanes (i), aromatic hydrocarbons (a), phenols (p) and the thiophenes (s) are marked
356 B. Horsfield
coupled with the fact that the method takes no account of the inert kerogen
fraction, question whether the relative abundances of the major pyrolysis
products are representative of the kerogen as a whole, and/or whether the
products are representative of the volatile fraction that in nature evolves as
petroleum. In this discussion the latter item is particularly important.
Horsfield (1989) determined aromaticities for a large suite of coal macerals
and kerogens using the relative proportions of major aromatic (hydrocarbon
and alkylphenol) and aliphatic (n-alkenes and n-alkanes) compounds in high-
temperature pyrolysates, and found that these values, when plotted against
atomic H/C ratio, fall on exactly the same trend as the fa-HIC trend from
published 13C-NMR literature. The remarkable overlap (Fig. 6.1O) provided
firm evidence that structural information is contained within the readily
identifiable and major components of pyrolysis products. The agreement be-
tween 13C-NMR and pyrolysis-GC was particularly good for kerogens with H/C
ratios less than 1.1, as was illustrated by the excellent agreement for the vi-
trinite and sporinite samples (see inset) that were common to both datasets.
The divergence in trends above H/C ratios of 1.1 is probably linked to 13C_
0.8
o o
0.6 TORBANITE 4 ql1
"/ .
1.6 "
Best fit ' ... .of>
'~."
o lines through /~/#
o o
1.2 total / " -1-
Key: data sets ~""
Hie h/
o = published f. vs.
relationships 0.8 ;0. SPORINITE 13
;,;'~VITRINITE 11
• = composition of pyrolysate ;'
Fig. 6.10. The relationship between kerogen aromaticity and atomic H/C ratio according to
13 C-NMR and pyrolysis-GC (Horsfield 1989)
The Bulk Composition of First-Formed Petroleum in Source Rocks 357
6.4.2
Simulating Catagenesis
6.5
Pyrolysates and Petroleum
This section describes the major classes of compounds seen in kerogen pyrol-
ysates and further examines whether these same products are seen in natural
petroleums.
The Bulk Composition of First-Formed Petroleum in Source Rocks 359
6.5.1
Aliphatic Hydrocarbons
500
n-Eicosan
0)
400
OJ
Q.
E 300
Sl
OJ
0;
2 200
0
N
U
Z:
100 0 0.1 K/min
300 320 340 360 380 400 420 440 460 480 500 520
Temperature (Degree C)
1400
2-Methy lthiophene
®
Qi'
15. 1200
E
Sl
(J)
1000
0>
,3
(j)
c 800
(j)
£
0.
0 600
E
>-
r: 400
GJ 0 0.1 Klmin
:;:;
0J 200
.• 0.7 Klmin
5.0 Klmin
0
280 300 320 340 360 380 400 420 440 460 480 500 520 540
Temperature (Degree C)
Kerogen~R
Path 1 Path 2
1 1
Kerogen ~ + 'V\IV'\R Kerogen /'v'V\A. + ~ R
lsomerisation Intermolecular
and or H-transfer
Decomposition
I I
Path A PathB
1 1
Alkene + radical Alkane
Fig. 6.12. Generalised reaction pathway for the formation of n-alkenes and n-alkanes in open-
system pyrolysates. (Kiran and Gillham 1976)
6
a
'"0
P P 0
;:;..
'"
Step 1 Step 1 o·
A
10 19 ::l
4 V II II II~ 0
14 I I u-+J I I A '""
P
...~
~
AI I I ~
16 0
...
aro
p..
A I! I! I! I! II H I I I I I 11111111r-L I! III 11111 II II II III! fllrllldllo I BilL 1.11.1 .111.1 I I I I I I I 11111 >-0
ro
::i
0
rb
1'0
AI IP
a
5·
Step 2 0
'"
Step 2 II ...1'0n
ro
:;.:;
0
A n
A P ~
6
I '"
10 14
4 V II II II~, 19 II I I P
Fig. 6.l3. Two-step pyrolysis-GC of Torbanite and Talang Akar Coal. Step 1,320-450 DC; step 2, 450-600 DC. n-Alkyl precursors in torbanite W
0-.
have a "homogeneous" distribution whereas those in the coal are "heterogeneous" (Horsfield 1989) W
364 B. Horsfield
et al. 1983; Curry and Simpler 1988; 0ygard et al. 1988; Muscio et al. 1991;
Horsfield et al. 1992).
Alkylcycloalkane moieties in kerogens may be released as such during
pyrolysis or retained in condensed and aromatised pyrolysis residues. Where
present in high-temperature pyrolysates they are usually only minor con-
stituents. For instance, they make up only a small proportion of high-tem-
perature pyrolysates from algal kerogens. In the case of Gloeocapsomorpha-
containing kerogens they display a strong odd carbon predominance in the C9 -
C19 range similar to the n-alkanes and cycloalkanes in related natural petro-
leums (Klesment 1974; Reed et al. 1986; Williams et al. 1988). In the case of the
Alum Shale and Bakken Shale it has been noted that alkylcycloalkanes made up
a higher proportion oflow-temperature closed-system pyrolysates than they do
of high-temperature open-system pyrolysates (Horsfield et al. 1992; Muscio et
al. 1994). This is in agreement with the results of oil shale pyrolysis where high-
temperature products contain the highest yields of aromatics and alkenes and
lowest yields of alkanes and char (Burnham and Happe 1984). It is also note-
worthy that alicyclic moieties in some algal lacustrine kerogens form involatile
aromatised residues on pyrolysis (Schenk et al. 1993). Fossil resins are pri-
marily alicyclic. Those from gymnosperms are diterpenoid whilst those from
angiosperms (e.g. dammar resin) are sesquiterpenoid (Alexander et al. 1987;
van Aarssen et al. 1990, 1991, 1992). Interestingly the closed-system artificial
maturation products of dammar resin yielded an abundance of 1,6 di-
methylnaphthalene, 1,6 dimethyl, 4-isopropyl-naphthalene, 1,6 dimethyl, 4-
isopropyl-decahydronaphthalene and bicadinanes, these also being prominent
components of Southeast Asian crude oils (van Aarssen et al. 1991). The latter
observation indicates that reaction mechanisms involved in the catagenesis of
fossil resins are similar to those performed in the laboratory.
6.5.2
Aromatic Compounds
The major resolved aromatic pyrolysis products in all kerogen types are the
CO-C2 alkylbenzenes and alkylphenols. In most type I kerogens the contribu-
tions are very small compared to the n-alkenes and -anes. Phenolic building
blocks constitute an even smaller part of type I kerogens, with proportions
purportedly increasing in response to increasing salinity (Derenne et al. 1992),
the degree of their cross-linking and hydroxylation/oxidation during early
diagenesis (Horsfield et al. 1994; Curry and Horsfield, unpublished data) and
the carbon skeleton (polymethylene, polyterpenoid or polyisoprenoid) of
polyunsaturated lipids entering into neocondensation reactions (Cane and
Albion 1971; Larter 1978; Metzger et al. 1985; Derenne et al. 1988, 1989). Type
II kerogens contain higher proportions of aromatics than do type I kerogens
(Fig. 6.9), with aromatic hydrocarbons being major components and phenols
present in only very low abundance. Toluene and the xylenes are prominent in
the vast bulk of cases, with amounts equalling or exceeding those of n-hy-
drocarbons in the same boiling range. The Alum Shale generates exceptionally
high yields of aromatics because of its unusual molecular structure (Dahl et al.
The Bulk Composition of First-Formed Petroleum in Source Rocks 365
1988; Lewan and Buchardt 1989; Horsfield et al. 1992). Also unusual are the
Bakken and Duvernay Shales (Devonian) of the Williston and Western Canada
Basins (Gray et al. 1991; Requejo et al. 1992; Muscio et al. 1994) and the
Womble Shale (Ordovician) of Oklahoma (Douglas et al. 1991). Petro-
graphically consisting of bituminite and alginite, these kerogens yield abun-
dant l,2,3,4-tetramethylbenzene by ~-cleavage of aromatic carotenoid residues
of photosynthetic sulphur-oxidising bacteria (Radke 1987; Requejo et al. 1992).
Additionally, type II-S kerogen yields l,2,3-trimethylbenzene when pyrolysed,
possibly from aromatised ~-~-carotene (Hartgers et al. 1994). At low levels of
naturally and artificially induced thermal stress, increasing maturation gen-
erally causes a fall in the abundance of aromatic moieties in pyrolysates (Van
Graas et al. 1981; Bjor0y et al. 1988; Boreham and Powell 1991; Muscio et al.
1994), ostensibly because aromatic-rich bitumen is expelled or the aromatic
systems become non-volatilisable as the case may be. While type II kerogens
generate higher absolute quantities of aromatic hydrocarbons on pyrolysis,
type III vitrinitic kerogens yield the highest relative amounts so that their
pyrolysates are dominated by alkylbenzenes, alkylnaphthalenes and alkylphe-
nols (Larter and Senftle 1985). These products originate from the pyrolytic
degradation of lignin, sporopollenin and polycarboxylic acids (Stout and Boon
1994). Coals of increasing rank yield pyrolysates that are progressively en-
riched in total and low molecular weight aromatic compounds (Romovacek
and Kubat 1968; McHugh et al. 1976), reflecting the aromatisation of the coal
macromolecule. Contemporaneously there is a decrease in phenolic structures
associated with the loss of oxygenated species during catagenesis so that
phenolic oxygen is essentially absent in coals of low volatile bituminous rank
(Van Graas et al. 1981; Senftle et al. 1986).
The fate of aromatic and naphthenoaromatic moieties during laboratory
pyrolysis and natural maturation is one of either cracking to form a volatile
component or condensation and its retention in the macromolecular structure.
In the laboratory, cracking reactions via ~-cleavage relative to the aromatic
ring are certainly favoured, resulting in a high abundance of mono- and dia-
romatic compounds, whereas their natural fate is not known with certainty.
The problem is not quantitatively significant for most type I kerogens because
aromatic component abundances are low. In the case of type II kerogens, there
is an empirical relationship between pyrolysate- and petroleum compositions,
with aromatic components making a pronounced contribution in both cases.
Thus, the paraffinic-naphthenic and paraffinic-aromatic oil families in nature
(Tissot and Welte 1978) could be related to the paraffinic-naphthenic-aromatic
pyrolysate family of kerogen pyrolysates by Horsfield (1989). Perhaps coin-
cidentally, toluene and meta-xylene are the most abundant single aromatic
compounds in both this oil type and pyrolysates of parent kerogens. The
remaining aromatic hydrocarbons do not occur as major distinct peaks in gas
chromatograms of either unaltered "marine" crude oils (e.g. Illich et al. 1977;
Bockmeulen et al. 1983; Thompson 1988; Williams et al. 1988) or their source
rock pyrolysates. In the case of crude oils they occur as di- through polyaro-
matics in the gas oil, lubricating oil and residuum fractions (Hunt 1979; Radke
1987). Aromatics therefore seem to be generated from the non-condensed
366 B. Horsfield
® Bakken Shale
--
":!!?
0,
25
original
c- c-
-
3 20 _(j' ~a~e r-
-r- -- -- c- ---
r-
_. c-
-- ..
....: r-
::I
E 15 . -. -. .- ..
(I)
u
c 10
2
c
I
0
() 5
I
()
0
I-
0 I I
0.31 0.55 0.68 0.72 0.90 0.92 0.94 0.99 1.11 1.26 1.57
Maturity (% R)
® Alum Shale
Conversion to ________~1,8~
%~__~2;7~
%~----~33%
DeodCorbon
l l +
300
C
<D
~200
-
~
0>
0>
EIOO
o
Maturity (T/72 hr)
Fig. 6.14A,B. The postulated neo-formation of inert carbon. A During natural catagenesis of
the Bakken Shale (Muscio and Horsfield 1996). B During the MSSV pyrolysis of Alum Shale
kerogen (Horsfield et al. 1992). (Reprinted with kind permission from Muscio GPA and
Horsfield B, Enhanced formation of inert carbon during the natural maturation of the marine
source rock; Bakken Shale, pp 10-16, 1996. American Chemical Society)
6.5.3
Sulphur-Containing Compounds
The major resolved sulphur compounds in kerogen pyrolysates are H2S, COS
and S02, which make up the gas peak in gas chromatograms, and the al-
kylthiophenes and alkylated benzothiophenes which dominate the C6 + fraction;
alkylated dibenzothiophenes and alkylthiolanes are also present but in smaller
abundances (Sinninghe-Damste et al. 1989). The carbon skeletons of the al-
kylthiophenes possess straight-chain, branched-chain, hopanoid and steroid
configurations and are formed during early diagenesis by intermolecular sul-
phur incorporation reactions involving functionalised lipids and hydrogen
sulphide (Brassell et al. 1986; Sinninghe Damste and de Leeuw 1990). The yield
of sulphur compounds from pyrolysis is directly proportional to the organic
sulphur content of kerogens (see above, Sect. 6.4.1). Thus, high-sulphur
kerogens from clay-poor depositional settings yield abundant sulphur com-
pounds on pyrolysis whereas kerogens deposited in freshwater or in the pres-
ence of excess reactive iron yield only small quantities (Eglinton et al. 1990b).
Sulphur-rich kerogens are usually also hydrogen-rich and classified as type II-S
(Orr 1986), though instances have also been reported of sulphur-rich type I and
type III kerogens (Sinninghe Damste et al. 1992, 1993; Radke and Willsch
1993). Sulphur-containing products from type I kerogens are dominated by the
2-alkylthiophenes and those from type II-S kerogens by the 2,5 dialkylthio-
phenes whereas those from coals and type III kerogens consist dominantly of
branched isomers such as 2,4 and 3,4 dialkylthiophenes (Eglinton et al. 1992).
Maturation may also play an influence, as exemplified by the decreasing ratio
of 2-methylthiophenel2,5 dimethylthiophene during the MSSV pyrolysis of
Posidonia Shale (transformation ratios >40%). Changes in the relative abun-
dances of 2,3 dimethylthiophene, 2-ethyl,5-methylthiophene and 2,3,5 tri-
methylthiophene have been documented for the Posidonia Shale (Ro = 0.48-
1.45%; Muscio et al. 1991). Maturation sequences from the Monterey Forma-
tion, Kimmeridge Clay and Mahakam Delta, supplemented by simulated ma-
turation results on corresponding immature samples, showed decreasing
thiophene ratios (2,3 dimethylthiophene/(o-xylene + n-non-1-ene)} and in-
creasing proportions of branched versus linear isomers (Eglinton et al. 1990b).
An increase in the alkylbenzothiophene lalkylthiophene ratio was also re-
The Bulk Composition of First-Formed Petroleum in Source Rocks 369
6.5.4
"Unresolved" Compounds
Pyrolysates Petroleums
~ Oil in reservoir cores
.A. Flash (SOO' C) L..:...;J Block 7/12
• Rock Eval
DSTs
• Hydrous (270-350' C) Block 34/10
o 20 40 60 80 100
Saturates %
Fig. 6.15. The bulk chemical composition of kerogen pyrolysates (origin stated within the
ternary diagram), petroleum from drill-stem tests (34/10 area, North Sea) and reservoir bi-
tumens (7/12 area, North Sea). All kerogen pyrolysates are richer in polar components, ir-
respective of their origins or the pyrolysis method used
The Bulk Composition of First-Formed Petroleum in Source Rocks 371
than is seen in naturally occurring solvent extracts (cf. Cornford et al. 1983;
Rowland et al. 1986).
One plausible explanation for the compositional discrepancy is that mi-
gration in the subsurface tends to concentrate hydrocarbons in the reservoirs
and polar components in the source rocks (Tissot and Welte 1978). In other
words, products generated in the laboratory and during natural petroleum
generation might be compositionally similar, but fractionation could lead to
crude oils becoming enriched in hydrocarbons. There is no doubt that this is a
contributory factor. However, the generally high expulsion efficiencies asso-
ciated with mature oil-prone source rocks (Cooles et al. 1986; Larter 1988) and
the hydrocarbon-dominated nature of most mature source rock extracts
(Philippi 1965; Powell 1975) demonstrate that kerogen decomposition in the
subsurface, not simply migration phenomena, produces a hydrocarbon-
dominated C1S + fraction. It can therefore be deduced that laboratory pyrolysis
generates products which in quantitative terms are quite unlike those derived
from natural maturation.
The Bakken Shale is an ideal material for studying the nature of polar
pyrolysate components because both flash pyrolysis and MSSV pyrolysis of its
kerogen yield 1,2,3,4 tetramethylbenzene as a distinctive and prominent
component (Muscio et al. 1994). Using this compound as a tracer it can be
shown that macromolecular polar materials in pyrolysates contain the same
precursor moieties that occur in the parent kerogen. Specifically, the open-
system pyrolysis of a bitumen, collected from a MSSV experiment (330 DC/2
days) produced a series of n-alkenes and -anes plus the notable presence of
1,2,3,4 tetramethyl benzene from its macromolecular components (Fig. 6.16).
These results dearly demonstrate that structural information contained in the
resolved alkenes/-anes and aromatic hydrocarbons of pyrolysates is also pre-
sent in the higher molecular weight bitumen fractions. This observation, also
reported for coal tars (Koplick et al. 1983; Nelson 1987), is consistent with the
macromolecular part of the polar fraction consisting of oligomeric fragments
of the kerogen or aggregates of small molecules.
6.5.5
Model of Kerogen Decomposition
350~ • }
~ ~ "
}. 330.C}.
2 days
} 2 days
l
MSSV Pyrolysis Solvent Extraction
> MSSV Pyrolysis On-line GC
.--.l
c:
II' 7
0
a.
(/)
>4 17 !!'
§.
Q) 17
(/)
c:
oa. .
(/)
~ I
10 20 30 40 50 60 70
I
0 - "0- 20 30 40-' '50- 60---70 - I'fomn
reten tion tim e (Min) retention time (Min)
!='"
::r:
Fig. 6.16. Experiments reveal that the GC-unamenable polar bitumen generated on pyrolysis contains the same types of ....oen
moieties as occur in the GC-amenable fraction. Here, bitumen collected from a 330 °C/3-day MSSV pyrolysis experiment [
was pyrolysed and yielded inter alia 1,2,3,4 tetramethylbenzene, a major pyrolysate component of Bakken Shale kerogen 0..
The Bulk Composition of First-Formed Petroleum in Source Rocks 373
Crude Oils
R.H R.Ar.H
Ar.H Hydrocarbons
Inert Reactive
Kerogen Kerogen
(R.Ar. RS.As.H)n
•
(A.Ar.As.As.~)n - ~
R.H R.Ar. Ar.H Hydrocarbons
6.6
Predicting Petroleum Compositions
6.6.1
Qualitative Versus Quantitative Predictions
20
mV Possibility 1 : RESOLVED C:!+ products only
18 plus methane (not shown)
15
Fig. 6.18. The gas-oil ratio of pyrolysates can be calculated using either resolved products
from a skim integration (upper) or from total products above baseline (lower)
376 B. Horsfield
(Fig. 6.18 lower part). The oil fraction consists largely of unresolved peaks in
the form of a hump above which can be discerned resolved components
dominated by n-alkenes, n-alkanes, alkylaromatic hydrocarbons and, in the
case of coals, alkylphenols. The unresolved components make up between 40
and 60% of the C6 + chromatogram for types II and III kerogens heated up to
transformation ratios of 0.70.
The analysis of a large sample set (see Horsfield 1989) reveals that gas-oil
ratios from all organic matter types (I, II and III) and origins (marine, la-
custrine etc) are uniformly very low and fall in the narrow range <0.4 kg/kg
(Fig. 6.19B). The average value (ca. 0.2 kg/kg) is in good agreement with
previously published values obtained by pyrolysis (Mann et al. 1987; England
and Mackenzie 1989). Because this value also corresponds to that of solution
gas-oil ratios in undersaturated marine-source rock-derived petroleums (also
see Bailey et al. 1974; Glas0 1980), it has been argued that this pyrolysis
method is indeed a good way of assessing the gas-oil ratio of petroleums
generated in marine source rocks, and that the broad range of GOR seen in
most petroleum provinces is linked to fractionations occurring during expul-
sion, secondary migration and dysmigration. Accepting for the moment that
these arguments are valid, it can be seen from Fig. 6.19B that all first-formed
petroleums should have very low gas-oil ratios, no matter what type of source
rock is involved, be they marine, paralic or non-marine. One specific con-
0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.8 2.0 2.2
Gas-Oil Ratlo
Fig.6.19A,B. Gas-oil ratios (C)-C S/C6 +) of pyrolysates from a variety of kerogen types. A
Based on resolved components only. B Based on total products, largely unresolved. (Horsfield
1989)
The Bulk Composition of First-Formed Petroleum in Source Rocks 377
sequence of this would be that all humic coals are oil-prone, and that the gas-
prone nature of petroleums associated with coals is due to the secondary
cracking of oil that could not cannot migrate from micropores (see Levine
1993). While this mechanism indeed operates to some degree - bituminous
coal extracts are extremely rich in involatile polar components - this does not
mean that C6 + pyrolysate is a measure of these component yields. Indeed,
coming back to the point made earlier, it is conceptually erroneous to calculate
gas-oil ratio from the quotient of C1-C5 /C 6 + products. The distribution of what
can be termed gas versus oil in the laboratory K~B reaction is not necessarily
the same as in the B~O reaction (Horsfield and Diippenbecker 1991). In
particular, "unresolved" components equating to "oil" (C 6 +) in the bitumen B
are likely to yield both oil and gas in nature, as inferred by the heating ex-
periments on Bakken Shale kerogen (Fig. 6.16).
An alternative way of directly calculating GOR from on-line pyrolysate data
is to utilise only the resolved components (Fig. 6.18 upper part) because, as
described above, their chain length distribution and paraffinicity are empiri-
cally related to those of genetically related natural petroleums. Two points then
emerge. First, GORs are higher by an average factor of 3 (Fig. 6.19A), and fall
mainly in the range 0.2-1.2 kg/kg. Such GORs give more conservative esti-
mates of relative oil yield and therefore of undersaturated petroleum occur-
rence than do those from total pyrolysates (Diippenbecker and Horsfield 1990).
Secondly, a relationship between GOR and source rock type begins to emerge,
with lacustrine petroleums predicted to have the lowest GORs, marine petro-
leums intermediate values and deltaic petroleums the highest. Such a result is
in line with organic facies concepts where petroleum composition and sedi-
mentary facies are closely linked (Jones 1987). It was this consideration that led
Diippenbecker and Horsfield (1990) to measure GORs by the skim method, and
these were used when modelling petroleum generation in the Posidonia Shale
of northwestern Germany instead of the total pyrolysate approach (Diippen-
becker and Welte 1991). Transformation ratios were predicted by a kinetic
model, and the GOR of the generated petroleum calculated using the labora-
tory-determined (MSSV pyrolysis) relationship between GOR and transfor-
mation ratio. Even these GOR values might be considered minima because the
aromatic content of petroleums are overemphasised by pyrolysis predictions
(see earlier). To some degree this effect is counterbalanced because on-line
pyrolysis takes no account of the macromolecular oil fraction, but this effect is
relatively minor because asphaltenes make up only a minor proportion of most
petroleums (Cornford 1993; Wilhelms and Larter 1994).
In summary, it is presently unrealistic to imagine that bulk petroleum
compositions can be determined quantitatively and directly using pyrolysis
because (1) the nature of the unresolved "hump" in pyrolysates remains
problematic and (2) the natural fate of aromatic and sulphur-containing
moieties is poorly understood, with the result that heavy oil generation and the
petroleum potential of coal are especially difficult to evaluate. The similarity
between the solution GORs of natural petroleums and marine kerogen pyrol-
ysate GORs appears to be coincidence. GOR based on resolved components
might be a temporary "prediction engineering" solution to this problem.
378 B. Horsfield
6.6.2
Organofacies Based on Petroleum Composition
Now that some of the deficiencies of quantitative pyrolysis data have been
explored, this section reviews how qualitative approaches may be used to infer
the link between bulk petroleum compositions, kerogen compositions and
depositional environment.
In recent years "determining organic facies" has become synonymous with
evaluating the composition and concentration of organic matter within a given
sediment as it is, or was, in its immature stage. The term "organic facies" has
been used in an alarming variety of contexts and connotations (Jones 1987),
but these boil down to two basic usages. One seeks to relate variations in
organic matter compositions and concentrations to specific biological inputs
and depositional processes, and thence recognise "anoxic and oxic facies",
"marine and deltaic facies", and the like. This involves the integration of
detailed geological information with, inter alia, organic petrographic and
biomarker data. Details can be found in treatises by Reading et al. (1978) and
Walker (1979) on sedimentology, Peters and Moldowan (1993) on biomarkers
and Chapter 5 (this Vol.) on organic sedimentation. The second usage focussed
on here, is to apply the information in a practical way. Because dramatic
chemical and physical transformations and mass transfer processes ensue
under "mild" temperature conditions «200 DC; see metamorphic processes), it
is logical that organofacies should be defined according to criteria that allow
the transformation of the static kerogen phase into mobile products, such as
petroleum, to be defined qualitatively and quantitatively.
Whereas Jones (1987) defined and mapped organofacies according to petro-
leum yield potential, this chapter deals with predicting the composition of
petroleums using the pyrolysate classification scheme of Horsfield (1989; see
also Cooper and Barnard 1984; Horsfield 1984; Larter and Senftle 1985; Orr
1986). Gas/condensate-, paraffinic-naphthenic-aromatic crude oil (high- and
low-wax varieties) and paraffinic crude oil generating (high- and low-wax
varieties) potentials have been recognised (Fig. 6.20) and are described below.
Similarities between these divisions and those of naturally occurring crude oils,
as described by Tissot and Welte (1978) are pointed out where appropriate.
The divisions of Jones (1987) are also included where feasible.
Woodford Shale and Toarcian Shale pyrolysates define the low-wax, mixed-
base crude oil generating facies. In nature the petroleums they generate belong
to the paraffinic-naphthenic and aromatic-intermediate classes. The low-wax,
mixed-base crude oil generating facies consists of black laminated shales and
carbonates with a high petroleum-generating potential (Jones' facies B). The
organic matter is derived mainly from algal and bacterial inputs though ter-
rigenous macerals such as sporinite and inertinite are common. This facies
most likely forms in silled basins and on stagnant shelves where reducing
The Bulk Composition of First-Formed Petroleum in Source Rocks 379
P·N-AOII
Low Wax
Fig. 6.20. The empirical relationship between petroleum types, source depositional environ-
ment and pyrolysate composition for clastic petroleum systems. (Newly calibrated after
Horsfield 1989)
The low-wax, paraffinic oil category is named after the composition of Ordo-
vician oils in the Michigan Basin (paraffinic class of Tissot and Welte 1978) and
380 B. Horsfield
The "high-wax paraffinic" field was named after the composition of Uinta
Basin oils (paraffinic class of Tissot and Welte 1978) and defined using pyrol-
ysates of the lacustrine Green River Shale. The high-wax, paraffinic crude oil
generating facies is a well-documented source of high-wax oil in the Tertiary
freshwater and saline lacustrine deposits of Asia, Australasia and the United
States (Hu 1985; Hong et al. 1986; Moore et al. 1986; Powell 1986). This facies
grades into, and may intercalate with, the gas/condensate- and high-wax,
mixed-base crude oil generating facies described above. The kerogen consists
of the remains of algae (Botryococcus) and bacteria and is a prolific petroleum
source (Jones' facies A). A stable stratified water column, as controlled by
salinity and temperature gradients and therefore by climate and topography, is
required to form this facies.
Lacustrine sediments may be deposited under oxic through anoxic condi-
tions and within saline through freshwater environments. The Laney Shale
member of the Green River Shale Formation (Washakie Basin) was deposited
in a hydrologically closed, alkaline lake under an arid climate and was char-
acterised by high concentrations (6-20% TOC) of alginite-rich organic matter.
The Luman Tongue member, on the other hand, was deposited in a hydro-
logically open freshwater lake under a humid climate and consisted of rela-
tively organic-poor (1-5% TOC) deep-lake mudstones and coaly lake-margin
sediments (see Horsfield et al. 1993b, 1994; Schenk et al. 1993). Three major
sequences occur in the Laney, corresponding to early lake deepening, max-
imum lake extension and a late rejuvenation phase that followed a period of
desiccation. The highest wax contents are associated with the first and third of
these, whereas the middle sequence (all are immature; Ro<OA%) has a pyrol-
ysate wax content approaching that of the low-wax, mixed-base crude oil
generating facies (Fig. 6.21). Interestingly, the deep-lake sediments of the
freshwater Luman Tongue member fall within the same trend as the alkaline
Laney Shale member. It can be concluded from this that alkalinity does not
exert a major influence on the chain length distribution of n-alkane precursors
in lake sediments.
Chain length distribution has been linked to redox conditions in the case of
relatively organic-poor (0.9-2.2% TOC) Cretaceous lacustrine sediments from
the eastern Alps (Sachsenhofer et al. 1996). Short-chain lengths characterised
the pyrolysates of organic-poor hydrogen-sparse bioturbated marls and re-
The Bulk Composition of First-Formed Petroleum in Source Rocks 381
LESS OXIC
C'5+
80%
F;atalllnie
High Wax
011-=3
Cl - Cs
100%
Fig. 6.21. Inferred petroleum compositions in lacustrine environments. Oxicity has a strong
bearing on source rock composition and hence likely petroleum composition in the Styrian
Basin (Sachsenhofer et al. 1996). Alkalinity has no measurable effect in the Washakie Basin
(Horsfield et al. 1994): crosses, freshwater lake; triangles, alkaline lake
382 B. Horsfield
Coal of the deltaic member of the Talang Akar Formation is the source of waxy
oil, gas and condensate in the Ardjuna Basin and was used to define the
boundaries of the high-wax, paraffinic-naphthenic-aromatic crude oil gen-
erating facies. This sub-class of high-wax oils, not recognised in the classifi-
cation scheme of Tissot and Welte (1978), usually occurs in lower delta plain
and inner shelf environments and commonly grades into and intercalates with
the high-wax paraffinic crude oil facies described above. The organic matter
often has a variable type II/Ill to type III composition and therefore falls in
facies BC and C of Jones (1987). The kerogen consists of vitrinite, cutinite,
liptodetrinite and resinite in variable proportions, and is derived in part from
lignocellulosic materials, preserved and partially degraded cuticular tissue and
plant resins, which give phenolic compounds, long-chain n-alkanes and
naphthenoaromatic compounds on analytical pyrolysis. Maceral abundances
are thought to be strongly influenced by the actions of meandering river
channels and tidal currents which erode peat deposits and segregate the
macerals (Thompson et al. 1985). Many Tertiary coals from Southeast Asia and
Australia fall in this category (Thomas 1982; Gordon 1985; Kelley et al. 1985).
Chain length distributions may be maturity-sensitive according to two-step
pyrolysis data, with long chains being released in preference to short ones with
increasing maturation (Horsfield 1989).
Gas/Condensate-Generating Facies
deltaic settings such as in swamps on lake margins or on the delta plain. When
total petroleum-generating potential is low (facies C and CD of Jones 1987),
telocollinite, sporinite and inertinite are the predominant macerals. This is
typified by the Carboniferous of northwestern Europe (e.g. Scheidt and Littke
1989). When total petroleum-generating potential is high (facies Band BC),
desmocollinite and resinite are usually the major macerals present. This is a
common feature of Southeast Asian coals.
The analysis of Westphalian coals (Krooss et al. 1995) revealed that the yield
of pyrolysis gases falls by almost an order of magnitude in going from high
volatile bituminous to meta-anthracite rank. This is exemplified by methane
yields which fell from 33-50 mg/g TOC at low rank to <5 mg/g TOC at high
rank. Primary gas potential may be estimated from open-system pyrolysis
whereas primary and secondary gas yields can be determined from closed-
system pyrolysis. The most significant differences in gas yield between the
open and closed methods occur for those coals containing labile alkylaromatic
and/or aliphatic moieties, this corresponding to the Ro range <1.4% where the
structure is open through "liquid", according to Hirsch (1954). In the open-
system, pyrolysis products are swept from the heated zone and to a large
degree reflect the types of structures in the parent material. In the closed-
system, first-formed products remain in the heated zone and react further to
form secondary products. Thus, as an example, alkylaromatic moieties cracked
from the coal molecule during open-system pyrolysis may be further trans-
formed to yield hydrocarbon gases (from methylene and methyl substituents)
and a polyaromatic residue upon further thermal degradation under closed-
system conditions. The yield of methane from the coal is between five and ten
times more than from type II marine kerogen of equivalent rank whereas the
yields of wet gas are about the same.
Surprisingly, the organic-rich alginitic type II marine shales of the Bakken
and Alum Shales also belong to this facies. In both cases the confirmation of
light hydrocarbon-generating capacity was afforded by thermovaporisation-
Gc. In the case of the Alum Shale, aliphatic carbon was abundant in the
kerogen structure but was not released as such during pyrolysis, there being a
predominance of Cj -C9 aliphatics and mono- plus dialkylaromatics. MSSV
pyrolysis experiments also revealed the contemporaneous formation of poly-
aromatic "dead carbon". While radiation damage might account for cross-
linking and thence aromatisation/condensation on pyrolysis (Dahl et al. 1988;
Lewan and Buchardt 1989) primary biological structures, possibly carotenoid-
like, represent a viable alternative (Horsfield et al. 1992). The case of the
immature Bakken Shale is similar in that alkylaromatic hydrocarbons and
enhanced "dead carbon" formation are associated with pyrolysis (Muscio and
Horsfield 1996). Up to 30% of originally volatilisable carbon may be trans-
formed into involatile aromatic structures during natural maturation accord-
ing to this experimental evidence (Fig. 6.14). Mass balance models which
assume that involatile carbon remains constant through maturation (Larter
1985; Cooles et al. 1986) will therefore give overestimates petroleum yields in
these cases.
384 B. Horsfield
Cf
(J
30
'\ ""('
t " 'Tj
::;.
~
lp'" .!n
o
CJ' •• '"
3
,
~'17 C6 - C,4 p..
'"
~
t~l ...""
o
ro
~
~ +
()
a a
~~a~ s·
", C/)
"V o
~
...
n
0.35...--------------------,
1-1
0.3
J 0.25
;; 0.2
o
~ 0.15
t 0.1 • Kerogen
0.05 • Asphaltenes
• NSO Compounds
o
WEN WlC DIE DOH HAR HAD
0.48 0.53 0.68 0.73 0.88 1.45 % Rm
Fig. 6.23. Changes in the gas-oil ratios (C)-C S/C6 + total components) of pyrolysates from
kerogens, asphaltenes and resins from the Posidonia Shale at different levels of maturity.
(Reprinted from Basin Modelling: advances and applications, Horsfield et aI., Kerogen typing
concepts designed for the quantitative geochemical evaluation of petroleum potential, 1993,
pp 243-249, with kind permission from Elsevier Science Publishers - NL Sara Burgerhartstraat
25, 1055 KV Amsterdam, The Netherlands)
NC6-14
o 100
PyrolysiS temperatures:
• 300"C
& 330"C
• 350"C
20 40 60 80
Fig. 6.24. Chain length distribution of n-alkanes in MSSV pyrolysates of immature Posidonia
Shale kerogen and Holzener Asphaltkalk asphaltenes (Horsfield et al. 1993). (Reprinted from
Basin Modelling: advances and applications, Horsfield et aI., Kerogen typing concepts de-
signed for the quantitative geochemical evaluation of petroleum potential, 1993, pp 243-249,
with kind permission from Elsevier Science Publishers - NL Sara Burgerhartstraat 25, 1055 KV
Amsterdam, The Netherlands)
had a GOR close to 0.2 kg/kg based on pyrolysis-GC data for Holzener As-
phaltkalk asphaltenes (Heckers, unpublished results) and Posidonia Shale
kerogens and asphaltenes, and equating buoyancy and capillary pressure, an
original oil column of 100 m was estimated (Horsfield et al. 1991). Petroleum
density, water density and interfacial tension values were calculated using a
maximum temperature of 100°C and a hydrostatic pressure of up to 15 MPa.
The amount of petroleum lost during alteration was calculated assuming that
The Bulk Composition of First-Formed Petroleum in Source Rocks 387
the gross C15 + composition of Posidonia Shale derived crude oils (Lower
Saxony Basin) and the Holzener Asphaltkalk were representative of the un-
altered starting material and altered end-product, respectively, that no polar
components were added during biodegradation, and that the total amount of
C1+ original petroleum could be inferred from the ratio of light to heavy
products (C I5 )C I5 +) from pyrolysis. The mass balance calculation revealed that
a 50-90% mass loss of petroleum could be attributed to alteration phenomena.
GOR values of 0.2 kg/kg and lower were considered. Figure 6.19 indicates this
GOR range is valid, even allowing for an algal lacustrine co-source.
These preliminary findings pointed to macromolecular organic matter in
petroleum accumulations, seeps and stains as being a source of data from
which the basin modeller might determine, on the one hand, kerogen type/
source facies and, on the other, gross compositional characteristics of the
original unaltered petroleum expelled from the source rock.
Asphaltic Oils
Toluene (%)
100 80 60 40 20 0
0 100
0 100
20
Interme9l~te
0"'·
,.:> CJ.
..
ij .
-01'
~
~:,....
40 0::;0 60 i?
...-t:
~p
r..
~ ~. ~
~.
0
.gJ ",
I01·~dphur ~
.oo~
~\\I
60 40 ......t:::
~~
~.
r.. Sol
t::: 80
~
.
\, Oil A
,
'l
100 0
100 0
0 20 40 60 80 100
C1S+ (%)
Fig. 6.25. The chain length distribution diagram (right), based on clastic petroleum system
correlations (Horsfield 1989), cannot distinguish between sulphur-rich heavy oil potential and
normal marine oil (paraffinic-naphthenic-aromatic) potential. Utilisation of sulphur-com-
pound abundance in pyrolysates allows high-sulphur from low-sulphur petroleum potential to
be recognised. (di Primio and Horsfield 1996)
•• II , ~ /'
y
•
y 300-375°C 450-600°C
Iy
c
••
p 80
70
Q. 60
"I..
> 50
'j
• :; 40
E 30
•
a 20 •
•
0' .«<
4j 46 47 48 49 50 51 52 53 54 55 56 57 58 j9
from that of the pyrolysis products, since the major proportion of high mo-
lecular weight compounds of aromatic/asphaltic oils are thermally involatile
and therefore cracked to secondary products during pyrolysis. High yields of
low molecular weight alkylthiophenes signify only that the kerogen is rich in
sulphur, and it is left to known correlations to infer bulk oil composition. At
higher energies, in which the dominant activation energy is included, the
pyrolysates contain higher proportions of n-alkanes/alkenes with a fixed chain
length distribution and lower sulphur contents, which in nature would be
manifested as higher API oils.
6.7
Concluding Remarks
me formulate the ideas expressed in this publication. Grateful thanks are also extended to a
great many friends and colleagues in industry and academia whose encouragement and/or
sponsorship has allowed this research theme to be pursued.
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Chapter 7
Petroleum Migration: Mechanisms, Pathways,
Efficiencies and Numerical Simulations
Chapter 7: Overview and Insights
During the past decade considerable progress has been made in unraveling
migration effects and processes. This has been due mainly to thoroughly
selecting and studying proper geological settings relevant to petroleum mi-
gration and by ingenious methods for investigating the geochemical effects of
migration on hydrocarbon and nonhydrocarbon mixtures. The range of
geological settings investigated reached from the microscopic to the regional
scale, from typical pore size distributions of source rocks to macroscopic
fractures and faults, and finally to specific case histories.
The strict comparison of migration phenomena between thick and thin
source beds, between hydrocarbon depleted and enriched rock segments,
between siliciclastic and calcareous source rocks has revealed very valuable
information confirming and refining the concept of a hydrocarbon phase
movement. Mass balance studies down to the molecular level suggest for rich
source rocks high expulsion efficiencies of more than 80%. All this in -
formation together with aspects derived from petroleum engineering has
been incorporated into a comprehensive approach on numerical simulation
of petroleum migration.
An implementation of numerical modeling of petroleum migration as an
integrated part of basin modeling has been achieved only recently. The main
reason for this time delay has been the fact that existing equations and
models for fluid flow in porous media, such as those applied in reservoir
simulation for many years, offered no easy connection to current basin
modeling systems. Meanwhile the proper geological and mathematical si-
mulation tools have been developed, connecting the modeling of polyphasic
fluid flow and basin modeling. The numerical simulation of petroleum mi-
gration presented here incorporates fluid flow of the three phases water, oil,
and gas and compositional changes in each phase. This compositional con-
cept is also applied in the framework of a multiple source rock concept which
allows tracing of petroleum from different sources throughout the entire
migration history. The fluid flow simulation model includes transport in
separate phases and also transport by diffusion. The petroleum migration
models differ from "classical" fluid flow problems in applied mechanics -
and these include reservoir modeling - mainly due to the fact that two
additional processes are integrated. Firstly, the thermally induced generation
of oil and gas introduces an additional fluid source into the model, and
secondly deposition, compaction, and other geological processes cause
pressure build-up, which acts as a driving force for fluid movement. The
effects of these processes are included in our migration concept and are
implemented in the flow equations.
Modeling of petroleum migration as understood here is not only a de-
scription of fluid velocities and flow paths but also takes into account the
transient changes induced by ongoing geological processes throughout the
matrix of sedimentary rocks. Some of these processes and their im-
plementation in the numerical analysis are discussed in more detail. Those
include: fault modeling, salt doming, rock fracturing, cementation of pores,
solution, and exsolution of light hydrocarbons in the aqueous pore fluid. The
incorporation of such processes in migration modeling allows a fairly rea-
listic simulation of different geological scenarios in context with the as-
sessment of the formation of petroleum accumulations.
Petroleum Migration: Mechanisms, Pathways,
Efficiencies and Numerical Simulations
U. MannI, T. Hantschee, R.G. Schaefer\ B. Krooss\ D. Leythaeuser3 , R. Littke\
and R.F. Sachsenhofer4
7.1
Introduction
Movement of petroleum from the source via carrier bed to the reservoir rocks
is called migration. This is divided into primary migration, defined as the
movement of oil and gas through and out of the fine-grained source rocks, and
secondary migration, the movement through wider pores in carrier and re-
servoir rocks to the trap. (Not discussed here are the aspects of petroleum
entrapment, redistribution in traps and petroleum loss from traps - generally
called "dismigration" - or the various types of traps.) In addition to petroleum
generation, petroleum migration is the principal process in the formation of
explorable petroleum accumulations (which, however, represent only a special
case of petroleum migration in which an otherwise diffuse fluid flow field is
highly focussed towards a reservoir structure).
An understanding how and why petroleum migration is sometimes focussed
to form a petroleum accumulation would require a four-dimensional (x, y, z
and time-lapse) reconstruction of the characteristics of migration pathways -
i.e. its rock and fluid properties - as a function of the palaeohistory of a
sedimentary basin. Although such a complete reconstruction represents an
idealisation that will never be reached, many significant recent developments
have elucidated the basic problems of petroleum migration. These concern the
mechanisms, timing, pathways and efficiency of petroleum migration. In total,
this has been obtained only by the consecutive integration of:
- sedimentology and petrophysics in order to identify and quantify the ca-
pacity of a pathway,
- organic geochemistry in order to establish migration mechanism, stage and
efficiency, and
- numerical simulation in order to reconstruct the petroleum migration
process within the geological framework.
1Institut fiir Erdal und Organische Geochemie (ICG-4), Forschungszentrum Jiilich GmbH,
52425 Jiilich, Germany
2 IES Gesellschaft flir Integrierte Explorationssysteme mbH, Bastionstr. 11-19, 52428 Jiilich,
Germany
3Geologisches Institut, Universitat zu Kaln, Ziilpicher Str. 49a, 50674 Kaln, Germany
4 Institut fiir Geowissenschaften, Montan-Universitat Leoben, 8700 Leoben, Austria
7.2
Migration Mechanisms
7.2.1
Primary Migration Mechanisms
The most important form of primary migration during the main phase of oil
and gas formation is discrete hydrocarbon phase movement (Dickey 1975;
Hunt 1979; Momper 1978; Tissot and Welte 1984; Welte 1987; Durand 1988;
Ungerer 1990; Mann 1994). However, as true hydrocarbon flow cannot take
place in micro- and mesopores of a source rock, and petroleum must yet reach
the macropores, diffusion directly after petroleum generation is the most likely
initial mechanism until a pressure-driven flow takes over (Fig. 7.l).
Hydrocarbon Generation
mechanism
Diffusion within
kerogen network
Flow within
pore space
Hydrocarbon Expulsion
Fig. 7.1. Mechanisms and place of mechanisms acting during primary migration (Mann 1994)
If oil droplets block the pore openings in a source rock, the water trapped
behind the oil expands as the temperature rises. The increased pressure caused
by the thermal expansion of water has been termed aquathermal pressuring by
Barker (1972). This mechanism should be responsible for abnormal pore
pressures primarily in shallow, impermeable sediments, particularly in areas of
high geothermal gradients (Daines 1982).
408 U. Mann et al.
Other Mechanisms
7.2.2
Secondary Migration Mechanisms
migrate along a tortuous pathway, always following the path of least resis-
tance, i.e. through that part of the rock with the largest interconnected pore
throats. Thus a continuous migration of oil stringers occurs as long as hy-
drocarbons are expelled from the source rock, and as long as oil droplets
coalesce to form new stringers. These principles have been elaborated by
Gussow (1954); Hobson (1954); Poulet (1968); Berg (1975); Hobson and Tir-
atsoo (1975) and Schowalter (1979). England et al. (1987) calculated that pet-
roleum must fill about 50% of the pore volume of a carrier bed or between 1
and 10% of the total cross section of the carrier bed before an interconnected
pathway for hydrocarbon migration is established.
The pattern of migration pathways under hydrostatic conditions was ela-
borated by Pratsch (1982). Using empirical data from many sedimentary
basins, he concluded that secondary migration starts at the depocentres of a
basin (where the most mature source rocks can be assumed) and continues
along migration pathways which follow the geometry of the individual sedi-
mentary basin to the basin edges (Fig. 7.2). This allows differentiation be-
tween those parts of a basin where petroleum migration is focussed, and
where it is dispersed. However, these migration patterns do not take into
account the lateral discontinuity of source and carrier rocks or a specific
tectonic situation.
Secondary migration occurs under varying pT conditions. Underway, a
change in conditions may cause precipitation of asphaltenes. Bitumens with a
composition rich in heavier and longer chain compounds are retarded by the
carrier, and a fraction with lighter and shorter chain compounds move on to
the reservoir. Compositional evidence for such processes is provided by case
histories reported for example by Wilhelms and Larter (1994a,b).
According to the individual geological situation, path length and flux rates
for secondary migration vary. Observed rates of oil migration in experiments
(around 10-50 ms- l ) were much higher than parametric estimates of basin-
scale oil migration (around 10-9 ms- l ; England et al. 1987) although this
corresponds well to flux rates of several meters per 100 years for a 100 mD
carrier bed (1 darcy = 10- 12 m2 ) as shown by experimental results (Thomas
and Clouse 1995). Core flood experiments by Selle et al. (1993) have in-
vestigated secondary migration through real rocks at a more realistic (for the
North Sea) dip angle of 7S. These experiments produced geologically plau-
sible, but still high, migration rates (10- 2 ms- l ) and showed the influence of
capillary forces. On the other hand, in a high permeability rock, with low
threshold capillary pressures (e.g. Bentheimer Sandstone with 2260 mD) Selle
et al. (1993) found secondary migration to be dominated by buoyancy forces.
It appears evident that the limitations for secondary migration are not the
flux rates, but the time necessary to create the minimum oil saturations within
the carrier rock. An understanding of secondary migration cannot assume
unlimited flow capacity due to an infinite source. Thus, for actual source rock
release rates, it would take more time to develop the critical saturation than for
the secondary migration process along the carrier bed. The rate-limiting step in
charging a reservoir is not secondary migration itself but rather the rate of
petroleum release from the source rock.
410 U. Mann et al.
circular asymmetrical
con tour lim:-::, 01 Ihl.: ~rlJul\I,J :turJ"aJ:1:
area ofrlo!'i,':hargc
Fig. 7.2. Migration pathways according to the geometry of the sedimentary basin under hy-
drostatic conditions. (Pratsch 1982)
Petroleum Migration: Mechanisms, Pathways, Efficiencies and Numerical Simulations 411
7.3
Migration Pathways
Recent drilling into vertical fault zones in the Gulf of Mexico (Durham 1994;
Anderson et al. 1994) brought attention to a new type of possible future ex-
ploration target: active migration pathways (Fig. 7.3). Active migration path-
ways demonstrate the essential conditions for petroleum migration to result in
an exploitable accumulation: high and concentrated flow rates. Further, it
shows that there are still other types of exploration targets than a conventional
reservoir. Direct evidence for active and ancient migration pathways as well as
potential migration pathways of different scales are evaluated in the following
two sections.
7.3.1
Potential Migration Pathways
Start and End Points of the Migration Pathway: The Role of Oil-Source Rock
Correlation
~
Eugene Island
Block 330
I
I
I
I
"7
...-,
growlh raulL:
aClive secondary
migration path
( coasta l Plain )
depos it s
Fig. 7.3. Drilling into an active secondary migration pathway. Sketch of hydro stratigraphic
model for migration and seal conditions in growth-faulted reservoir and how secondary mi-
gration of hydrocarbons occurs through the fault zone at Eugene Island Block 330, Gulf of
Mexico. (Durham 1994, courtesy of Flemings, Penn State University)
Petroleum Migration: Mechanisms, Pathways, Efficiencies and Numerical Simulations 413
Table 7.1. Summary of some established oil-oil and oil-source rock correlation parameters
Basic parameters:
n-Alkane predominance Even Odd None
Sulphur content High (1-5%) Variable «2%) Low «0.3)
SAT/ARO Low-medium Medium-high High
Ni, Vcontent High Low-high (1-2) Low or absent
NiIV-ratio Low (::;1) Low (::;1) High (>2) only for
lacustrine sources
Pristane/phytane Low «1) High (> 1) Very high (>3)
Pristane/n-C 17 High (>0.6) Low «0.6) High (>0.6)
Phytane/n-C 18 High (>0.3) Low «0.3) Low
Biomarkers
General
Sterane predominance C27 >C 29 High C28 , C27 <C 29 High C29
(also diasteranes
and mono aromatic
steroids)
C30/(C27-C30) steranes High Low Low
Diasterane/regular sterane Low-moderate Moderate-high Medium-high
SteraneI17a(H)-hopane Low High Low
Oleanane index None None Since Lower
Cretaceous
Specific environment
,-Cerane index For high salinity
4-Methylsteranes For dinoflagellates
C3s -Homohopane index Degree oxic
environment
Carbon isotopes
Type curves (sat. -+ oil ---7 Heavier Heavier Heavier
extract ---7 kerogen---7
aro. ---7 NSO---7
asphaltenes)
Isotope profile Light-heavy Light-heavy-light Heavy-light
Several authors (Bally 1975; Stonely 1981; Green 1983; Kingston et al. 1983)
have attempted to explain the relationships between the geodynamic (tectonic)
situation of a sedimentary basin and hydrocarbon flow. The evaluations have
in common that three principal migration systems can be differentiated ac-
cording to three major types of sedimentary basins.
The fault migration system (Fig. 7.4 top) is associated with continental rift
basins (pull-apart basins and back-arc basins). High tectonic subsidence rates
and high heat flow cause the rapid deposition and maturation of source rocks.
Petroleum migrates predominantly in vertical direction along a network of
frequently reactivated faults. The presence of permeable fractures in source
rocks supports the vertical petroleum transport but also encourages dismig-
414 U. Mann et al.
ration and leakage. Temporarily closed faults do not only stop migration but
provide individual tectonic compartments with high overpressures.
Long-range migration systems (Fig. 7.4 middle) are found primarily in older
cratonic basins. These basins have been very stable during relatively long time
periods with low subsidence rates and low heat flows. The number of source
rock layers is generally very limited and often confined to one single strati-
graphic unit. Maturation levels sufficient for petroleum generation are often
reached only in the basin centre, whereas suitable traps for petroleum accu-
mulation occur at the basin edges. Shallow platforms built-up in the course of
these long time periods which include many hiatuses due to intervals of
nondeposition and erosion. These platforms provide relatively uniform carrier
and reservoir rocks. This fact and the repeated occurrence of seals favour short,
vertical, primary migration pathways and long-range lateral (secondary) mi-
gration routes. The long pathways provide large drainage areas. But the chance
for loss of relatively large proportions of petroleum as residual oils, tar mats
and tar sands is also substantial. Where the platform formations are litholo-
gically discontinuous, stratigraphic traps are common. Due to the shallow
overburden the chances for the formation of overpressure zones are low.
A widespread scatter of reservoired oil and gas within a sedimentary basin
is the result of dispersive migration systems. Dispersive migration systems
(Fig. 7.4 bottom) are predominantly encountered in basins situated in orogenic
belts which are areas of compression with active orogenesis. Orogenic belts
possess highly variable but often low geothermal gradients. Subsidence is
caused not only by gravity but also by tectonic movements. The dispersion of
oil accumulations is due to a migration system formed by rapid and hetero-
geneous sedimentation periods with resulting irregular sedimentation. This
geometry is not favourable for the formation of permeable, long-distance
migration pathways. Relatively short lateral and vertical migration paths
contribute to varying degrees. In addition, there is a high risk for dismigration
due to the ongoing orogeny and activation of faults. Therefore leakage, surface
shows and biodegraded oils occur frequently. One attraction of orogenic belts
is the existence of anticlinal trap situations. The intensity of the tectonic stress
and the resulting number of folds and faults per area determine the degree of
dispersion within such a migration system. Comparable heterogeneous sedi-
mentation patterns with the same implication for dispersive hydrocarbon
migration as in orogenic belts are also known from deltaic plays.
The overall possibility and efficiency for petroleum transport is related to the
timing of several individual processes during the geological evolution of a
sedimentary basin. Which processes are interrelated to petroleum migration is
best demonstrated by an events chart (Magoon and Dow 1994), a summary of
the evolution of a petroleum system. This chart relates the timing between the
following essential elements and processes: deposition of source, reservoir, seal
and overburden rock, trap formation, generation, migration and accumulation,
Petroleum Migration: Mechanisms, Pathways, Efficiencies and Numerical Simulations 415
Fig. 7.4. The three principal migration systems (fictitious case histories): fault migration
system, long-range migration system, dispersive migration system
416 U. Mann et al.
Geologic Ti me
400 300 200 \00 Scale
, ·cnts
Rc crvoir Rock
Seal Rock
Fig. 7.5. Events chart showing the relationship between the essential elements and processes
as well as the preservation time and critical moment for a fictitious petroleum system. (Ma-
goon and Dow 1994)
Petroleum Migration: Mechanisms, Pathways, Efficiencies and Numerical Simulations 417
r IDolomitization I
2 2
IIncreased acidityl J l
Petroleum generation JI
and migration
3 310n
Fig. 7.6. Synthesis for burial, maturation and diagenesis. (Schwarzkopf 1990)
418 U. Mann et al.
Secondary Porosity
Fig. 7.7a,b. Vertical fracture from Lower Toarcian Posidonia shale at 0.73%R r . a Normal light,
crossed nicols. Fracture fill bears calcite and solid bitumen. b Luminescence excitation. The
following phases can be identified according to their relative chronological sequence: solid
bitumen (BIT); light-orange luminescing calcite (eel, Fe 2+/Mn2+ ratio <0.3) and weakly dark-
orange luminescing calcite (ee2, Fe 2 +/Mn2+ ratio >5.7). At this position, the adjacent Posi-
donia shale is heavily dolomitisized (Dol). (Jochum 1993)
420 U. Mann et al.
via solution seams in carbonate, evaporite and siliceous source rocks from the
Palaeozoic to the Tertiary (Grabowski 1984; Palacas 1984; Mann 1994, 1996).
Reactions of "clay volatiles" with quartz or carbonate may also be able to
create secondary porosity for potential migration pathways. According to re-
sults of Heller-Kallai and co-workers (1987, 1988, 1989; Miloslavski et al. 1991;
Heller-Kallai and Miloslavski 1992), these volatiles form by thermal dissocia-
tion of clay minerals at individual temperature stages.
Fractures have been reported as migration conduits not only for hydrocarbons
which have left the source rock but especially also for petroleum expulsion
from source rocks (Meissner 1978; Littke and Rullkotter 1987; Talukdar et al.
1987; Leythaeuser et al. 1988c; Mann 1990; Mann et al. 1991). Fractures may
open and close several times due to stress cycling effects, also called "seismic
pumping" (Sibson et al. 1975). Fault/fracture meshes acting as conduits within
an extensional stress regime tend to form either as subvertical extensional
"chimneys", or "fuzzy" normal faults (Fig. 7.8). In the Monterey shales they
have acted as major fluid expulsion structures, transporting large volumes of
aqueous and hydrocarbon fluids across the bedding anisotropy, the relict mesh
structure being preserved through cementation by silica, carbonate, and bi-
tumen (Redwine 1981; Sibson 1994). In total, faults, extension fractures, and
stylolites can substantially affect permeability of the rock mass.
Expulsion Fractures
permeability (lOxmd)
o
-I
-2
-5
-6 overpressure
-7
-8
Fig. 7.9. Relationship between sedimentation rate and permeability in order to build-up
overpressure
422 U. Mann et al.
their organic matter content and small grain size source rocks are generally
highly ductile and therefore require a high excess pressure for fracturing. After
careful investigations most expulsion fractures turn out to be tectonic-induced
fractures. Because there is little petrographic evidence, many petroleum geol-
ogists are still sceptical that expulsion fractures act as migration pathways.
The findings about potential migration pathways from the core and basin scale
must be integrated into each other. This means a lateral extrapolation of the
facies from the core to the basin scale. System tracts from sequence strati-
graphy (see Chap. 1; Van Wagoner et al. 1990) provide a very high degree of
facies predictability in the subsurface. This predictability can be used for ex-
trapolations to the basin scale and applied within a numerical simulation of
petroleum migration to trace facies changes of carrier beds and subsequent
migration routes. During such an extrapolation correct up-scaling procedures
are important and must be developed without neglecting the anisotropy of a
sedimentary basin fill.
7.3.2
Evidence for Migration Pathways
High permeability provides the first direct evidence for a migration pathway.
After potential migration pathways have been qualitatively identified, effective
from less affected or noneffective pathways need to be distinguished. These
distinctions are generally based on direct and indirect permeability data si-
milar to the approach used by reservoir engineers. The following paragraphs
present both the principle objectives and limitations of such an approach.
The intrinsic permeability of rocks in the subsurface varies over more than
l3 orders of magnitude from 10- 10 m2 to about 10-23 m2 (Brace 1980; Bre-
derhoeft and Norton 1990). These values vary according to lithology, com-
paction and cementation/dissolution processes (Table 7.2). Pore size and
fracture width represent the main controlling agent for petroleum flow as
permeability is proportional to several powers of pore size or fracture width. It
is known that very few large pore channels need be present to have a dramatic
effect on permeability (e.g. Khanin 1968). Furthermore, different types of
migration mechanisms are involved at different pore size levels. Thus, it is
essential to determine the relative amounts of pore size classes present in a
representative rock sample from a migration pathway, especially to differ-
entiate between the low permeability domain of the source rock (dominated by
diffusion), the higher permeability domain of the source rock (dominated by
Petroleum Migration: Mechanisms, Pathways, Efficiencies and Numerical Simulations 423
Table 7.2. Permeability ranges for sedimentary, igneous and metamorphic rocks
Darcy flow), and the high permeability domain of the carrier rock (also
dominated by Darcy flow).
A classification of pores as a function of their size from rough pores to
ultramicropores is provided in Table 7.3 (according to the IUPAC classifica-
tion) by Singh et al. (1985), the supplement of ultramicropores by Dubinin
(1975) and the classification of macropores by Setzer (1977). A quantification is
possible by a combination of microscopy, mercury porosimetry, gas adsorp-
tion and other measurements (Table 7.4).
However, quantification of transport-related properties of rocks and fluids
requires the evaluation of the relative importance of three competitive forces:
viscosity, capillarity and gravity. Their importance varies according to the scale
of observation, for example, whether migration takes place at the source bed
where capillary forces prevail, or by transport through more permeable rocks
where gravity and viscosity forces predominate.
Table 7.3. Pore classification according to size (Singh et al. 1985; Dubinin 1975; Setzer 1977)
Total porosity
Calculation of apparent All Easy calculation
density
Image analysis d;?: 20 nm Pores of irregular Only area information,
shape measurable subjective measurements
Quantitative image d;?: 20 nm Optical check, even by Assumes spherical pores,
analysis TEM limited to large pores
Small angle X-ray 1nm::;d::;100nm Short-term method Complicated evaluation
scattering program
Small angle neutron 1 nm ::; d ::; 100 nm Short-term method Complicated evaluation
scattering program
Accessible porosity
Xylene and water d >100 nm Simple, short Small specimen, no pore
impregnation size distributions
Rubber or liquid metal True pore network No measurable pore size
impregnation skeleton distribution
AirlHe penetration Some nm Short, good No pore size distribution
reproducibility
N2 adsorption d < 50 nm Correlation to BET Physical model,
surface complicated evaluation
program
Mercury porosimetry 3.4 nm < d < 60 ~m Most extended range Assumes cylindrical
of pore size, pores
comparable data,
standard use
arbitrary values for the relative permeability versus oil saturation curves be-
cause they had been extrapolated from a production study. The principal
conclusion was correct, however, according to more recent results relative
permeability curves for source rocks differ considerably from conventional
curves for reservoir rocks (compare Fig. 7.10). This must be considered for
numerical modelling of expulsion processes. According to the calculations of
Okui and Waples (1993) the maximum oil saturation should not be higher than
25% (see Fig. 7.10). However, theoretical considerations and case studies show
that 15-25% is only the minimum oil saturation required for the beginning of
the expulsion process (Welte 1987; Mann 1994). Measured oil saturations of
the pore space around peak oil window are in the range between 40% and 60%
(Mann et al. 1991; Ropertz 1994; Mann 1996). Variations seem to be effected
predominantly by the range of porosity which act as a buffer and may thus
even retard petroleum expulsion for a limited time.
A
0.0 -I--,--..,...--=,--,--'-,--,--='¥--,--,----1
o 20 40 60 80 100
Swirr Swc
WATER SATURATION (%)
20 40 60 80 100
WATERSATURATION(%)
Fig. 7.10. Relative permeabiltiy curve for a typical reservoir rock (A) compared to that for a
typical shale source rock (B), as proposed by Okui and Waples (1993)
Petroleum Migration: Mechanisms, Pathways, Efficiencies and Numerical Simulations 429
The main concepts to understanding two-phase fluid flow in the high per-
meability domain of carrier and reservoir rocks are the concepts of capillary
pressure (Leverett 1941), relative permeability (Amyx et al. 1960) and wett-
ability (Craig 1971). These fundamental concepts for secondary migration
represent the effective flow behaviour as a function of fluidlfluid and fluid/rock
interactions. Accordingly, rock and fluid properties are of fundamental im-
portance during migration (see Sects. 7.4.2, 7.5).
The movement of petroleum during secondary migration, the principles of
buoyant rise and capillary displacement, under hydrostatic and under hydro-
dynamic conditions are also described by Tissot and Welte (1980, p. 341ff, and
references therein). The process of oil movement can be summarised as fol-
lows. For migration under hydrostatic conditions, buoyant forces of the pet-
roleum phase must become high enough to overcome the capillary resistance
430 U. Mann et al.
Oil seeps at outcrops or oil-stainings at drill cores are the first direct and most
obvious indications for petroleum migration pathways. Nevertheless, beside
the "classical" occurrence from source to trap, there exist several specific
settings where hydrocarbons and bitumens may occur (Fig. 7.11). Asphalt-like
bitumen may itself serve as caprock (e.g. Levorsen 1967, p. 336). Bitumens are
also found in a wide range of ore deposits, where they are generally used as
evidence for an active role of hydrocarbons in ore genesis and a source of
information about the geothermal and geochemical conditions of mineralisa-
tion (Gize 1993). On the other hand, late stage bitumens may be completely
unrelated to the mineralisation process and simply used the same migration
pathway as the ore generating pore waters (Parnell 1991). Further, Simoneit
(1994) describes the paragenesis of bitumen together with hydrothermal fluid
systems associated with oceanic spreading centres.
The residual soluble organic matter in the source rock and, if available, the
comparison with its corresponding reservoir oil provide the key to elucidate
the type of process(es} that took place during primary migration and expul-
sion. For instance, in terms of hydrocarbon composition on the molecular level
a separate phase flow by bulk oil expulsion should exhibit no, or only little,
fractionation, whereas hydrocarbon transport by solution in water or gas as
well as diffusion show characteristic fractionation effects. To arrive at such
conclusions soluble organic matter must be extracted from the rock material
and separated by liquid and gas chromatography into compound groups,
homologous series, isomers and individual molecules, thus forming the basis
for mass balance calculations. In addition, concentrations of selected hydro-
carbon compound groups or individual molecules with distinctive chemical
and physical properties can be compared. For example, one must determine
the ratio of saturated hydrocarbons to aromatics, or both to non-hydrocarbons
(NSO compounds), more water-soluble aromatics versus less water-soluble
ones, or short-chain to long-chain hydrocarbons.
Present knowledge of primary migration processes is derived from theo-
retical considerations and experiments but predominantly from selected case
histories. Comparisons of live oil versus residual oil as well as source rock
systems of siliciclastic, carbonate, siliceous and evaporite lithologies are pre-
sented in Section 7.3.3. The main problem of this kind of investigations is the
need for well-characterised sample material, i.e. in general, conventional cores
or rock samples of adequate quality.
~ 'I vein ~
s::
0:>
::s
~: ':': :.:~::,>':~i>.:=-::}':(:::.~:':(::·}':(::}':(::~/(::~'«::~}~)}~)}(i~T:(::~i(~.~:iL.{rJ()~.(l': .~ .{ ~::t;\}t<:ri;tnn~T( ::s
~
~
Hydrothermal Setting "t:I
'"qo
open closed ro
c
3
'. ".". '. ' ' cO nd~n&1t.:: . t s:::
ciQ.
2000111 ":: "::. ~ plum.: S~d ll11"'l1tS or ....
,", water e;.
water .. ,.:....' dissipal ion
CO IU1111l
o·
Po
l phasc s:::
~ _ separation n
~ acclIJ'n ulalion '"
::r
;:l
'"0;.
Ilvdro-
thennal ~!~ 3
Y'
Fluid - ----
~ "t:I
:;-
'"
~tT:I
3'l
n
Atypical Setting :;;.
;:l
n
:;;.
'"
'";:l
p..
Z
c
3
....
'"r;.
so urce rock r--------...__
( immalllr~) L I_ _ _ _ __ _ - l l_ _
eo..
C/)
S·
se;.
.. I~
o·
;:l
'"
..,.
UJ
UJ
Fig. 7.11. Settings in which bitumens or paragenesis of bitumens with other phases occur
434 U. Mann et al.
Fig. 7.12. Calcite fracture fill in Lower Toarcian Posidonia shale (0.73 %Rr). Many fluorescing
petroleum inclusions are trapped in between crystal boundaries of calcite; crystal grow is
vertical to bedding
Fig. 7.13a,b. Micrograph of hydrocarbon-bearing fluid inclusions from a calcite fracture fill
from Lower Toarcian Posidonia shale at 0.88%R r. a Primary yellowish fluorescing hydro-
carbon inclusions within a calcite crystal which give homogenization temperatures of 75-
15°C. b Secondary yellowish and brownish fluorescing hydrocarbon inclusions along trails of
with calcite resealed microcracks which give homogenization temperatures of 50-85°C.
(Jochum 1993; Jochum et al. 1995)
Petroleum Migration: Mechanisms, Pathways, Efficiencies and Numerical Simulations 435
436 U. Mann et al.
7.3.3
Case Studies on Primary Migration
Until the end of the 1970s the knowledge about primary migration processes
was predominantly speculative and hypothetical. Roberts and Cordell (1980),
for instance, concluded that an adequate understanding of petroleum migra-
tion had not been achieved because of insufficient observations of petroleum
Petroleum Migration: Mechanisms, Pathways, Efficiencies and Numerical Simulations 437
a l cm
Fig. 7.14a,b. Vertical fracture from Lower Toarcian Posidonia shale at O.880/0R,. a Plug with
residual bitumen in the centre of a partly with calcite resealed fracture. b Cryo-SEM micro-
graph showing spherical holes in residual bitumen which are interpreted as formerly gas-filled
cavities formed by retrograde condensation during uplift of the source bed. (Mann et al. 1994b)
moving from one place to another in the subsurface, although numerous at-
tempts have been made by petroleum geoscientists to recognise petroleum
migration effects and to deduce a consistent theory.
A well-documented case history based on organic geochemical methods is
the Mahakam Delta area, off-shore Kalimantan, Indonesia (Durand and Oudin
1980; Vandenbroucke et al. 1983). Based on a comparison of hydrocarbon
compositions between oil pools at a wide depth range in a multiple-pay field
and those of the interbedded organic-rich shales and coals, migration was
concluded to have occurred in a vertical direction and over a considerable
438 U. Mann et al.
distance from a source interval deeper than the deepest oil accumulation. In
contrast to such regional studies, it was suspected that on a more local, or even
smaller, scale regular depth trends of the amount and composition of organic
compounds in source rocks may identify the drainage direction to the more
permeable carrier beds or other migration pathways. Likewise, Vandenbroucke
(1972) and Connan and Cassou (1980) studied drainage effects in source-rock
type shales near their contacts with porous reservoir beds. Later, in line with
the tremendous progress of analytical methods introduced in organic geo-
chemical research in the 1980s, other well-documented case histories were
presented by Mackenzie et al. (1983, 1987, 1988) and by Leythaeuser et al.
(1984a,b, 1988a,b,c).
Using a similar concept as Vandenbroucke (1972), Mackenzie et al. (1983)
and Leythaeuser et al. (1984a) investigated in detail migration effects in shale/
sandstone sequences of two cored boreholes from Spitsbergen Island, Svalbard,
which penetrated Lower Cretaceous and Palaeocene sequences, respectively.
Since the organic matter of the source beds is mainly land-plant derived, this
case study may serve as an example of type III kerogen at a maturity level with
vitrinite reflectance, Rn of about 0.8%. In terms of migration stage the patterns
of hydrocarbon composition allowed the classification of most samples ana-
lyzed in one of the four categories "unmodified" shales (i.e. samples that
contain all, or most, of their original bitumen due to unfavourable drainage
conditions), "unmodified" sandstones with no signs of enrichment by mi-
grated bitumen, "depleted" shales that have experienced expulsion or "en-
riched" sandstones and siltstones. Most interesting was the strong depletion of
thin interbedded shales and of the edges of thicker source rock intervals where
some samples showed a strong dependence of the degree of depletion in re-
lation to carbon number of, for example, the n-alkanes. This effect is typical for
diffusion-controlled and/or gas-driven migration mechanisms rather than for
movement of the n-alkanes in a continuous oil phase. The observed migration
phenomena led the authors to propose that the main phase of expulsion in
such sequences is preceded by a stage during which only the edges of thick
shale units and very thinly interbedded shales are depleted. This early expul-
sion is not a "pulsed event" but rather a slow and continuous process which is
associated with pronounced compositional fractionation effects. The authors
concluded also that their observations could explain the origin of accumula-
tions of light oils and gas-condensates discovered in many low-maturity se-
quences bearing predominantly terrestrial-derived organic matter.
Similar effects of petroleum expulsion from two source rock intervals
bearing type III and oil-prone type II kerogen, respectively, as a function of
their distance from more permeable carrier beds has been documented by
Leythaeuser and Schaefer (1984) and by Leythaeuser et al. (1984b) in a cored
well that penetrated Upper Carboniferous strata of Rr = 1.1 % in northern
Germany. The authors presented material-balance type comparisons of se-
lected samples extending from the centre portions of the two source rock units
to their outer edges. Progressive depletion in petroleum compounds towards
the more permeable adjacent layers could be shown clearly.
Petroleum Migration: Mechanisms, Pathways, Efficiencies and Numerical Simulations 439
WELL 1
DEPTII(m)
3950
WBLL2
4000 4000
4050 4050
4100 4100
4150 4150
Fig. 7.15. Geological column for both wells of the Brae Oilfield area and location of cored
sections studied by Mackenzie et al. (1987). Solid portions indicate zones of the Kimmeridge
Clay Formation selected for detailed study. (Reprinted from Petroleum Geology of North West
Europe, Mackenzie et al., The expulsion of petroleum from Kimmeridge clay source rocks in
the area of the Brae oilfield, UK continental shelf, pp 865-877, 1987, with kind permission
from Graham & Trotman Ltd., London SWI V IDE, England)
440 U. Mann et al.
able sandstone layers. The study was designed to assess the relative importance
of two principal mechanisms of primary migration, i.e. pressure-driven flow of
a discrete petroleum phase (see Durand et al. 1984) or diffusion of petroleum
molecules through the porous rock matrix. The organic geochemical analyses
were planned in such a way that the geochemical effects of petroleum expulsion
should best be recognised by comparison of samples which have experienced
different drainage conditions under natural conditions.
In detail, an approx. 13-m-thick interval of the Kimmeridge Clay formation
overlying a sandstone sequence (weIll, core 4) and an approx. 12 m thick shale
unit of same age sandwiched between two sandstone intervals (well 2, core 5/6)
were chosen for this purpose, including some very thin interbedded shales.
Additionally, a DST oil of well 1 [maturity in terms of vitrinite reflectance
equivalent (see Radke 1987) Rc = 0.75%] from the above-mentioned sandstone
sequence was made available for comparison. As a first step, screening-type
analyses based on Rock-Eval pyrolysis appeared suitable to determine migra-
tion effects in terms of total hydrocarbon depletion. As depicted in Fig. 7.16,
the so-called transformation ratio or production index (PI; see Espitalie et al.
1977) of the Kimmeridge Clay samples showed a clear tendency to decrease
4020
4114
4022
4116
4024
g 4026 ~
...l
4118 ~
...l
<: <:
~ 4028
::z::
(Il 4120
::z::
(Il
4030 4122
4032 4124
4034 4126
PRODUCTION INDEX
Fig. 7.16. Production index [SI/(SI+S2»)' also called transformation ratio, calculated from
Rock-Eval pyrolysis data (see Espitalie et al. 1977) versus depth for the two continuous shale
source rock (Kimmeridge Clay Formation) intervals (Leythaeuser et al. 1988a). SST, Sandstone
Petroleum Migration: Mechanisms, Pathways, Efficiencies and Numerical Simulations 441
towards the adjacent sandstone layers. In well 1 PI values decrease from about
0.20 at 4020 m depth to about 0.07 just above the sandstone, and in well 2 PI
values decrease from about 0.30 in the centre of the shale unit to about 0.15 at
the margins. Likewise, after solvent extraction of selected samples the plot of
both the total soluble organic matter and the C1S +-hydrocarbons after liquid
chromatography supported the screening data (Fig. 7.17).
The observed effects were interpreted as follows for this typical geological
situation that comprises an oil-prone source rock in a favourable condition
with respect to generation and expulsion. Petroleum is expelled chiefly as a
petroleum-rich phase driven by excess pressures once such a phase fills most of
the pores of the source rock. Therefore, the expulsion of n-alkanes, for in-
stance, was nearly independent of their carbon number. There were distinct
differences in composition, however, between the bitumen or "residual oil" in
the source rock and the expelled reservoir oil, as is seen in Fig. 7.18. Frac-
tionation processes have caused the relative depletion of the latter in non-
hydrocarbons and the relative enrichment in saturated hydrocarbons, whereby
the proportion in total aromatics was only slightly enhanced. This commonly
observed discrepancy in composition of crude oils and the (residual) bitumen
in their source rocks results from the chromatography-like retardation prop-
4020 Ell,
)1
-1
~
g
4024
~ J
is
~
.-/// 'f.
~ 4028 ~.
4032
Fig. 7.17a,b. Yield of C1s+-soluble organic matter and C1s+-hydrocarbons versus depth for the
two continuous shale source rock (Kimmeridge Clay Formation) intervals. (Leythaeuser et al.
1988a)
442 U. Mann et al.
E-<
rIl
,
0
Z
<
rIl
4112
~ 4116 1
t:3
~ 4120
> ~
>-l
<:
:r:
CI.l
4124
CD
E-<
4128 rIl
SHALE INIERVAL
0
Z
0 SOLUBLE ORG. MATIER <
rIl
4132 0 HYDROCARBONS
+ REFERENCE SAMPLE
20 40 60 80
C15+ - YIELD (mglg TOC) b
Fig. 7.17b
erties of the source rock matrix with respect to the more polar compound
groups of a bitumen.
In thin interbedded shales the depletion in saturated hydrocarbons was
extreme due to very favourable drainage conditions. The increasing depletion
of source rock intervals towards shale/sandstone contacts ("edge effects") and
the locally very high depletion of thin interbedded shales ("ideal drainage") are
caused mainly by capillary forces enabling additional bulk oil expulsion as a
separate phase flow. Obviously, capillary pressure differences cause oil spon-
taneously to drain from mudstones into adjacent sandstones, and water to
replace it is imbibed by the mudstone. The authors argued that it is not ne-
cessary to invoke fracturing for expulsion to occur: the pores were sufficiently
large for most petroleum flow to occur through primary porosity. This process,
Petroleum Migration: Mechanisms, Pathways, Efficiencies and Numerical Simulations 443
4020
4025
g
4030
4035
4040
4095
Fig. 7.18. Changes in yield and gross composition of C1 s+-soluble organic matter for selected
samples of Kimmeridge Clay Formation shales in comparison to gross composition of re-
servoir oil from underlying Brae sandstone unit. Diameter of circles for source rock samples is
proportional to yields of C 15+-soluble organic matter. (Leythaeuser et al. 1987)
5 SUB-SAMPLES
em
"STYLOLITE"
MATUrn1TYSEQUENCE
Well B
~4600m~ c
0.4911
- 5000 m D
0.65
-5800 m
VITRINITE REFLECTANCE
Rr(%)
-6200 m
0.90
Fig. 7.19. Sampling scheme of study performed by Leythaeuser et al. (1995), based on con-
ventional cores of a Triassic-age carbonate source rock formation from three wells re-
presenting different maturity levels. Most samples were subdivided into a solution-seam or
stylolite bearing portion and a clean micritic carbonate portion (termed "matrix"). (Reprinted
from Mar Petrol Geol, 12, Leythaeuser et al. Pressure solution in carbonate source rocks and
its control on petroleum generation and migration, 1995, pp 717-733, with kind permission
from Elsevier Science Ltd, The Boulevard, Langford Lane, Kidlington OX5 1GB, UK)
Toe contents of the samples from the Triassic source rock are low to
moderate, ranging between 0.2 and 0.4% for most samples. Although these
values are very low as compared to shaly source rocks, they fall within the
range of Toe data reported for many carbonate source rocks (Gehmann 1962;
Hunt 1979). For the well B and well e samples the Toe contents of the solution
seam and the stylolite bearing samples are significantly higher than those of the
adjacent carbonate matrix equivalents. To assess realistic values for the Toe
contents of pure stylolites or solution seams a "corrected" Toe content can be
Petroleum Migration: Mechanisms, Pathways, Efficiencies and Numerical Simulations 447
defined under the assumption that all carbonate had been removed from these
layers due to pressure solution processes:
TOCes = y /(1 - x)
2000
o~· 1
I
1600
V/
~!
.;;
1200
0=Jt.-.
+
800
~...
'?A
I
400 ~·B al
c
0--c:7·
1400
0/0/
J
1200
S
,e; 1000
~
800
600 ;'0
.~
400 • .----;-+
---I~·:=:.!----·
200
c~- b
~~;:;:;::::: .~
2000
~~'\
/':, ~" c:
/0
~/ II
1600 II 0 II
II 0 '\ \ II
1200 It
II 'III II
II
II D II ~ II
~ II II
800
•
II
II
~.I
400 6'~
c
0
0.1 0.2 0.3 0.4
ORGANIC CARBON (%)
Fig. 7.20. Yields (in mg/kg of rock) of C1s +-soluble organic matter (a) and C15+ hydrocarbons
(b) versus total organic carbon content for sample pairs of solution seam or stylolite bearing
and adjacent carbonate matrix subsamples. c Mean values calculated for the data shown in a
and the interpretation scheme of Leythaeuser et al. (1995). Open symbols, carbonate matrix
samples; filled symbols, solution seam or stylolite bearing samples. (Reprinted from Mar petrol
geol, 12, Leythaeuser et al. Pressure solution in carbonate source rocks and its control on
petroleum generation and migration, 1995, pp 717-733, with kind permission from Elsevier
Science Ltd, The Boulevard, Langford Lane, Kidlington OX5 1GB, UK)
Petroleum Migration: Mechanisms, Pathways, Efficiencies and Numerical Simulations 449
algae are here compacted, and, due to removal of carbonates, brought in close
contact with each other. Thus, as schematised in Fig. 7.21d, local zones of high
concentration of oil-prone organic matter are formed which, upon deeper
burial, allow the pore system of interval C-D to become oil-saturated and, due
to effective sealing, eventually over-pressurised. Figure 7.21e finally shows the
stage where the build-up of (over-)pressure has led to the formation of frac-
tures and their filling with petroleum fluids by lateral migration along the
stylolites or solution seams, respectively.
The validity of this model needs to be further verified by other case histories
although the results and interpretations presented by Sassen and co-workers
for the Smackover formation of the Gulf of Mexico basin (Sassen et al. 1987a,b;
Sassen 1988; Sass en and Moore 1988; Sassen 1990) lead to very similar con-
clusions.
Good to excellent biogenic siliceous source rocks are known from the Mon-
terey formation from the San Joaquin basin in California (e.g. Isaacs et al.
1983). Diagenetically altered and unaltered diatoms make up silica, porcella-
nites (opal-A and opal-CT) and quartz cherts (e.g. Graham and Williams 1985).
Such sedimentary constituents provide generally a high porosity, but at the
same time a relatively low permeability. This explains why many source rocks
of the Monterey formation are distinctive in yielding high SI signals from
Rock-Eval pyrolysis (Graham and Williams 1985), thus indicating abundant
generated liquid hydrocarbons, and why petroleum migration through the
macropore network has not been reported from the Monterey formation so far.
Primary migration in the Monterey shales has recently been evaluated by Lee
(1991). He observed oil-stained solution seams and fractures and concluded
that these are the pathways for primary migration. On the other hand, similar
observations were made in the reservoirs of the Monterey formation, where
production efficiency depends on the content of detrital material (Isaacs 1984)
and the resulting degree of fracture formation.
Evaporitic rocks as such, for instance anhydrites or halites, contain only
trace amounts of organic carbon (Connan et al. 1986). In this respect, such
pure evaporitic lithologies do not represent typical petroleum source rocks.
The petroleum potential of an evaporitic sequence arises from the fact that its
sedimentary column often comprises layers of siliciclastic and/or carbonate
sediments with their respective input of organic matter. Based on the particular
geological and palaeoclimatic conditions, evaporite sequences may even show
regular sedimentation cycles. The kerogen type in these sediments generally
reflects strongly anoxic environments during deposition, and main contribu-
tions to the organic matter is due to bacterial input. Sulphur-rich type II
kerogens are frequently encountered and give rise to early-mature heavy oils in
these source rock systems. Generally, evaporitic source rocks are associated
with close-range migration systems. They combine the petroleum source itself,
the reservoir rock and the cap rock on a local scale. Accordingly, primary
migration usually occurs along short migration pathways, whereby the mi-
450 U. Mann et al.
------------------c
------------------D
------------------8 a
~t~
· ·_ · ·_··_··_··_···_··_··_··_··_·__ A
· ·_·_
......----==------8
.1. .... . .. ..... .. ............. b e
volume reduction
by mechanical
....!....---------------- A compaction
kerogen particles
(e.g. algae)
clay minerals
carbonate
cementation by
carbonate redistribution
residual kerogen (center)
and halo of petroleum
-,----------------- B
J c
saturates pore space
Petroleum Migration: Mechanisms, Pathways, Efficiencies and Numerical Simulations 451
gration mechanism depends on the type of the source facies, i.e. its lithology
and the type of organic matter.
7.4
Migration Efficiency
7.4.1
Relative and Absolute Source Rock Expulsion Efficiency
Fig. 7.21a-e. Conceptual model by Leythaeuser et al. (1995) to explain the processes of pet-
roleum generation and migration and those of carbonate diagenesis by pressure solution. a
Stage I: initial sediment (lO-cm-thick interval) with rhythmic variation of ratio of carbonate to
non-carbonate matter. b Stage II: initial stage of formation of solution seam by pressure
solution upon burial to a few hundred metres depth. c Stage III: final stage of formation of
solution seam by pressure solution and mechanical compaction. d Stage IV: optimum stage of
petroleum generation due to kerogen decomposition, however, prior to primary migration. e
Stage V: petroleum expulsion by migration in lateral direction. For sake of simplicity, frac-
tures resulting from overpressuring are not shown in this scheme. (Reprinted from Mar Petrol
Geol, 12, Leythaeuser et al. Pressure solution in carbonate source rocks and its control on
petroleum generation and migration, 1995, pp 717-733, with kind permission from Elsevier
Science Ltd, The Boulevard, Langford Lane, Kidlington OX5 1GB, UK)
452 U. Mann et al.
stituents of mature source rock samples to their original immature state from
the same facies. Therefore the primary requirement of a mass balance is to
obtain a realistic idea of the composition of a presently mature source rock
unit before the maturation process started. Usually it is attempted to find an
immature equivalent of the source rock in question and use it as a reference.
Very often, however, this approach encounters severe limitations as no im-
mature equivalent of the source rock is available.
The main constituents of petroleum source rocks are the two solid phases,
mineral matrix and kerogen, which together represent more than 90% of the
total source rock mass. In rich source rocks the kerogen content amounts to
more than 10% of the total mass, and if the term source rock is extended to
coals, the solid organic matter content can even exceed the mineral content and
be the predominant fraction. In contrast, the extractable organic matter (bi-
tumen) and the low-molecular weight hydrocarbons usually represent only a
minor fraction of the total mass of a source rock. In a source rock mass balance
aimed at the reconstruction of petroleum generation and expulsion the four
source rock components mineral matrix, kerogen, bitumen and low-molecular
weight hydrocarbons must be quantified. The pore water contents of source
rocks are usually not reported because standard geochemical analysis is per-
formed with, and normalised to, dry samples. The LHC concentration in source
rocks, determined by thermovapourisation techniques (Schaefer and Littke
1988; Schaefer 1992), showed some degree of variability due to the volatility of
these compounds. However, as they represent only a minor fraction of the total
mass, this uncertainty usually does not affect the overall results of a mass
balance calculation to a significant extent.
Efforts to recognise and quantify the bulk compositional or molecular ef-
fects of petroleum expulsion by geochemical analysis have been made for more
than 20 years (e.g. Vandenbroucke 1972; Connan and Cassou 1980; Durand
and Oudin 1980; Vandenbroucke et al. 1983; Sajgo et al. 1983). Also, Leyt-
haeuser et al. (1980) studied hydrocarbon generation in selected source rocks
as a function of type and maturation. They presented a mass balance approach
in terms of organic carbon contents, subdivided into "hydrocarbon generation
potential", "carboxyl carbon" and "dead carbon", as well as the bitumen
contents, with maturity increase for the three main kerogen types. However,
since their data were based on a world-wide selection of source rocks, the need
for well-defined case histories with a better control of the organic facies, the
lithological characteristics and the geological framework became obvious.
The most basic mass balance approach assumes that the immature reference
sample corresponds exactly to the original state of the mature sample in terms
of organic carbon content, kerogen type, and initial extract yield. A respective
case history was conducted by Rullk6tter et al. (1988) in a multidisciplinary
approach. This study was based on four shallow boreholes drilled in the Hils
syncline of northern Germany to determine quantitatively the amount of
Petroleum Migration: Mechanisms, Pathways, Efficiencies and Numerical Simulations 453
WEN
/ 853.5 140.8
~l
, ,
0.48
DIE
/
"'-
853.5
Residue
94.2
~ .
112:0~ ~441 24.6
L088-
I
0.68
HAR
/ 853.5 65.4
1~1f1761
I
54.8 0.88
HAD
/ 853.5
Matrix
61.5
Kerogen
Ilf
Bit. CO2
20.8
I
61.9
Oil + Gas
1.45
Fig. 7.22. Mass balance for petroleum generation and expulsion from the carbonate-lean upper
unit of the Lias epsilon shale (Posidonia shale) in the Hils syncline, northern Germany. All
yields are normalized to 1 g initial rock of immature stage and assume no loss or gain in the
average amount of mineral matrix. (Reprinted from Advances in Organic Geochemistry 1987,
Rullkiitter et aI., Organic matter maturation under the influence of a deep intrusive heat source:
a natural experiment for quantitation of hydrocarbon generation and expulsion from a pet-
roleum source rock, (Toarcian Shale, northern Germany), 1988, pp 847-856, with kind per-
mission from Elsevier Science Ltd, The Boulevard, Langford Lane, Kidlington OXS 1GB, UK)
454 U. Mann et al.
plus gas reached a value of 86% at the end of the main generation stage
(Rr = 0.88%).
The data and conclusions of Rullkotter et al. (1988) are based on very
favourable geological and sampling conditions which are rarely found in other
regions of the world. Heating of an oil-prone source rock by a deep-seated
igneous intrusion is a unique natural experiment for the quantitation of the
effects of petroleum generation and expulsion. The important question whe-
ther their interpretations are equally valid in "normally" matured source rocks
in a subsiding basin, however, could not be answered conclusively.
In many instances the original organic matter content of source rocks at the
time of deposition has been subject to regional variations which could skew the
overall mass balance performed with these assumptions. Therefore Cooles et al.
(1986) proposed a mass balance scheme which takes the amount of "inert
kerogen" as a basis of reference for the calculation of petroleum generation
and expulsion efficiency. "Inert kerogen" denotes the fraction that cannot be
converted into petroleum due to the limited availability of hydrogen in the
organic matter. The inert kerogen content of individual samples of a given
source rock is assumed to be a measure of their original organic matter con-
tent. It can be assessed from the difference between the present TOC content
and the amounts of organic carbon residing in the bitumen and the "reactive
kerogen" of the sample.
As a quantitative measure of the progress of petroleum generation and
expulsion Cooles et al. (1986) defined the petroleum generation index (PGI)
and the petroleum expulsion efficiency (PEE) as follows:
PGI = (petroleum generated + initial petroleum)/(total petroleum potential)
PEE = (petroleum expelled)/(petroleum generated + initial petroleum)
Here, the "initial petroleum" denotes the "inherited bitumen" incorporated
into the kerogen at the beginning of the early-diagenetic processes after de-
position of the sediment. The bitumen content of the samples is either de-
termined by solvent extraction or by the Sl peak of the Rock-Eval procedure
whereas the reactive fraction of the kerogen corresponds to the S2 peak.
Figure 7.23 shows the reconstruction of the original composition of a pre-
sently mature source rock unit from an immature equivalent of the same
source rock. Solid frames indicate the parameters which can be determined
directly by the measurement of the TOC content, Rock-Eval pyrolysis, and
solvent extraction.
This mass balance scheme of Cooles et al. (1986) was applied to a number of
petroleum source rocks from different parts of the world, for example, the
Kimmeridge Clay formation of the North Sea or the Brown Limestone of the
Gulf of Suez. The petroleum expulsion efficiency was found to increase with
the calculated average initial potential of the source rock and to reach values
well above 80%. Expulsion efficiencies in excess of 50% were found even for
source rocks with an initial petroleum potential of less than 10 kg per tonne of
rock.
The approach of Cooles et al. (1986) retains the requirement of an identical
kerogen type in the study area but it renders the calculations independent of
"0
~
g.
'"
S
s::
1:
o
Po
1------------- .,.e,~J> s::
Bitumen II I' c,..."'t .~
(initial II '"S-
II '$f~. ~~
petroleum) II reactive kerogen El.
II ~.q;
II carbon ~
II
II "0
""
II
II bitumen carbon
CRKl*CW
""
II
CRK2 = ""
::===~r CIKl
tTj
reactive kerogen
reactive kerogen
carbon
f
Etl
(")
carbon
CRK3
g'
(")
~ (b'
.... 1 '"
CRKl ;;;;;; ------ ~
Cw A-
~ Cw
t-------'t; Z
inert kerogen
CIKl inert kerogen ~
carbon ;:l.
carbon (")
inert kerogen
carbon
e:..
' - -_ _ _ _ _ _--L- _ _ _ _ _ _ --'--_ _ _ _ _ _ _...J.. en
[
immature reference reconstructed original a..
mature sample o
sample state of mature sample ::l
'"
Whereas the previous examples are mainly based on the mass balance of
petroleum fractions rather than individual molecular species, other attempts
focussed on molecular aspects of the residual bitumen in the source rock and
the expelled and eventually accumulated petroleum to unravel the mechanisms
of primary migration. For example, in a Miocene-age sequence from the Ma-
hakam Delta region (Kalimantan, Indonesia) Vandenbroucke et al. (1983) have
compared hydrocarbon compositions and concentrations of interbedded or-
ganic-matter rich shales (including coal seams as potential source rocks) in the
multiple-pay Handil oilfield. Rock samples from the mature and overpressured
interval of this sequence were contrasted to less mature equivalents in the
hydrostatically pressured interval. The authors found depletion effects by ex-
pulsion in the order of 90% and 66% for the C6 -C9 and ClO-C 14 hydrocarbons,
respectively, whilst the concentrations of C2S -C 3S hydrocarbons remained
constant, i.e. pronounced compositional fractionations associated with ex-
pulsion was observed in this case history. The effects caused by pressure re-
lease during sampling, however, and their possible influence on the rather
volatile low and medium molecular weight hydrocarbons remained an open
question. This interpretative restriction is not confined to this particular case
history but pertains to all studies in which rock samples from deep wells are
depressurised during the sampling procedure.
As outlined above in more detail, Mackenzie et al. (1983) and Leythaeuser et
al. (1984a) investigated migration effects in Palaeocene-age type III kerogen
bearing source rocks with a maturity level in terms of vitrinite reflectance of
about 0.8%. Calculated relative expulsion efficiencies, defined as the con-
centration difference between an "unmodified" reference sample and a de-
pleted sample, divided by the concentration of the reference sample, decrease
with increasing carbon number for a thin shale sample (5 cm thickness).
Nearly 90% expulsion was calculated for n-C 1s H32 , but no significant expulsion
was suspected beyond n-C2s Hs2 (Fig. 7.24a). For thicker intervals the re-
spective values were not so extreme; however, the tendency of decreasing ex-
pulsion efficiencies with increasing carbon number of the n-alkanes was
generally observed in these type III kerogen bearing source rocks. Similar
Petroleum Migration: Mechanisms, Pathways, Efficiencies and Numerical Simulations 457
100~--------------------------------~
RD-62.S m
80
I 0.82 %Rr I
60
EARLY
KH-1l26.7m
I
\l.1%RrI
60
MAIN
40
20 I-
b 0 I
15 20 25 30 35
CARBON NUMBER
Fig. 7.24a,b. Comparison of relative expulsion efficiencies for C15 + n-alkanes as a function of
carbon number for selected samples of thin interbedded shale layers at different maturity
stages (Rr = 0.82 and 1.1%, respectively) for type III kerogen bearing source rocks. (Leyt-
haeuser et al. 1987)
results were demonstrated also at higher maturity (Rr = 1.1%) for a type III
kerogen bearing source rock of Carboniferous age (Leythaeuser and Schaefer
1984; Leythaeuser et al. 1984b). Relative expulsion efficiencies for a thin shale
layer (Fig. 7.24b) are about 80% between n-C 1s H32 and n-C 2o H 42 and decrease
sharply to higher molecular weights. A comparison of these results with those
458 U. Mann et al.
of a type II kerogen bearing source rock interval from the same borehole
showed that expulsion efficiencies at the edge of the source rock unit varied
between ca. 80% and 95%, with no tendency to decrease with increasing carbon
number.
Similar observations were made in a comprehensive study (see above) for
the Upper Jurassic Kimmeridge Clay formation, the most important oil-prone
source rock of the North Sea area (Mackenzie et al. 1987, 1988; Leythaeuser et
al. 1988a,b). Expulsion efficiencies for the n-alkanes were more or less in-
dependent of their chain length although the expulsion efficiencies showed a
clear tendency to increase (up to about 90%) when approaching the lithological
boundary between source rock and carrier bed (Fig. 7.25) as well as in the
special case of thin interbedded shales. It was concluded from this that for rich,
oil-prone source rocks, petroleum expulsion occurs as a single-phase petro-
leum fluid but not before a minimum saturation of the shale pore system has
been exceeded. For leaner quality source rocks with predominantly land-plant
derived organic matter, migration mechanisms are different. Since such source
rocks generate significant amounts of gas and lesser quantities of oil, the latter
is probably transported in gaseous and/or hydrous solution. Fractionation
effects, for example, according to chain length for the n-alkanes, result from
differences in vapour pressure or solubility (see Leythaeuser et al. 1987).
In carbonate source rocks, solution seams and stylolites have been sus-
pected repeatedly to serve as avenues for petroleum migration (Grabowski
4022.4m 4028.8m
40~----------~ -
-
I I
4030.8m 4033.4m
- - -
-r-- - - -
-r-- - - -
20 -r-- - - I-
I I
15 20 25 30 35 15 20 25 30 35
CARBON NUMBER
Fig. 7.25. Relative expulsion efficiencies for C1S + n-alkanes as a function of carbon number for
selected samples from the Kimmeridge Clay Formation. (Leythaeuser et al. 1987)
Petroleum Migration: Mechanisms, Pathways, Efficiencies and Numerical Simulations 459
1984; Palacas et al. 1984; Sassen et al. 1987a,b). Direct geochemical evidence for
this conclusion was provided by Leythaeuser et al. (1995) for a carbonate
source rock of Triassic age from northern Italy. Comparison and mass balance
of hydrocarbon yields of selected samples that have experienced enhanced
depletion versus those which have expelled petroleum to a lesser degree re-
present the key to recognise and quantify the effects of petroleum expulsion
and to deduce the nature of primary migration mechanisms.
Based on the case history for this carbonate source rock outlined in detail in
Section 7.3.3.2, Fig. 7.26 exemplifies this effect for stylolite bearing samples
from maturity stages Rr = 0.65 and 0.90% in wells C and D, respectively. The
quantities of well-defined compounds rather than total extracts or hydro-
carbon fractions including long-chain n-alkanes, pristane, and phytane were
chosen for this purpose. As is seen in Fig. 7.26a, the stylolite bearing sample
from well C has much higher n-alkane, pristane, and phytane yields than the
stylolite-bearing sample from well D. The difference in TOC content between
both samples cannot account for the observed hydrocarbon concentration
differences. Unless cracking reactions have played a dominant role, the op-
posite trend as a result of progressive generation would be expected. Therefore
the yield difference is interpreted to reflect mainly the effect of petroleum
expulsion from the stylolite of the well D sample. As in the examples for
siliciclastic rocks discussed previously, the calculated relative expulsion effi-
ciency denotes the ratio between the yield difference of a reference sample (well
C in this case) and a depleted sample (well D) divided by the yield of the
reference sample (well C).
The mass balance between both samples (Fig. 7.26b) reveals a smooth n-
alkane distribution envelope peaking at n-nonadecane, and pristane and
phytane in approximately equal proportions. Relative expulsion efficiency
values (Fig. 7.26c) remain fairly uniform within 60-80% in the molecular range
between n-heptadecane and n-pentacosane. For pristane and phytane, near-
equal expulsion efficiencies are observed as for their straight-chain isomers.
For oil-prone source rocks of siliciclastic lithologies the relative expulsion
efficiencies of n-alkanes which remain uniform with increasing carbon number
have been interpreted to indicate petroleum expulsion as a separate-phase fluid
(Mackenzie et al. 1987; Leythaeuser et al. 1988a). In contrast, n-alkanes from
gas-prone type III kerogen bearing source rocks reveal regularly decreasing
expulsion efficiencies of the n-alkanes with increasing carbon numbers, in
particular at lower maturities. This compositional fractionation as a function of
chain length is explained by migration of these petroleum components in
gaseous solution. The trend shown in Fig. 7.26c, however, represents more
analytical evidence for a continuous-phase oil migration, although the expul-
sion efficiencies decrease markedly both to the lower and the higher molecular
weight range. A continuous-phase oil migration had been postulated pre-
viously in the literature as the predominant mechanism of petroleum expulsion
from carbonate source rocks (Jones 1984).
The examples above show that expulsion efficiencies can vary greatly within
an individual source rock unit: They change as a function of proximity to
carrier beds and migration avenues and vary with compound type, molecular
460 U. Mann et al.
C
40
30
20
10
a
o~~~~~~~~~~~.-~
30
20
10
80
60
40
20
c
15 20 25 30
CARBON NUMBER
Fig. 7.26. a Concentration (in mg/kg rock) of normal and isoprenoid alkanes pristane and
phytane as a function of carbon number for stylolite bearing samples from well C (vitrinite
reflectance Rr = 0.65%) and well D (vitrinite reflectance Rr = 0.90%). b Concentration dif-
ference between both samples. c Relative expulsion efficiencies for well D sample. (Ley-
thaeuser et al. 1995). (Reprinted from Mar Petrol Geol, 12, Leythaeuser et al. Pressure solution
in carbonate source rocks and its control on petroleum generation and migration, 1995, pp
717-733, with kind permission from Elsevier Science Ltd, The Boulevard, Langford Lane,
Kidlington OX5 1GB, UK)
7.4.2
Efficiency of Secondary Migration
Table 7.5. Results of calculations for Malacca Strait Prospects (Mackenzie and Quigley 1988)
Table 7.6. Necessary oil saturations for oil breakthrough. (England et al. 1987)
and gas. However, they must admit an error bar of (0.01 m 3 /m 3 • The example
of the calculated charge volumes from Malacca Straits, Indonesia, shows that
because of the much longer migration distance in one prospect, the corre-
sponding high losses resulted in a negative charge volume (Table 7.5).
While distances can generally be assessed relative precisely from seismic
sections, more critical because of a much higher uncertainty are estimations of
the residual oil saturations. Residual oil saturations in carrier rocks are con-
trolled by the same rock and fluid properties as the required saturation to
permit the beginning ("breakthrough") in oil transport, hence initial and re-
sidual saturations are of equal size. At the place of the actual migration
pathway, saturation values range between 20% and more than 90% of the pore
volume (see Table 7.6); however, this concerns an equivalent of only 5-10% of
the total carrier rock volume which finally gives an apparent residual satura-
tion of only about 2% (Mackenzie and Quigley 1988). On the other hand,
Hirsch and Thompson (1995) claim that in a typical geological situation per-
meability is large enough to carry oil to the reservoir over geological time at
saturations of less than 1% of the pore volume. Such different values between
1% and 90% are predominantly an effect of the sedimentary fabric, i.e. small
scale heterogeneities and the pore size distribution of the carrier rock.
However, essential to the basic understanding of residual oil saturations are the
effects of the pore network within a rock.
Pore Network
A pore network is defined by the actual pores (sensu stricto) and the con-
necting (pore) throats. The three-dimensional, geometric relationship between
pores and throats controls beside the actual fluid flow also the amount of
residual oil. The three major variables are (Wardlaw 1979; Mann 1983, un-
published results): (a) the ratio of the pore radius to the throat radius (low
ratios give high, ratios close to 1 give low residual saturations); (b) co-
ordination number of throat(s) to one pore (lower coordination numbers give
higher residual saturations); (c) the type and level of heterogeneity of a pore
network (domains of small pore throats located within a network with large
throats are easily drained, but domains of large pore throats located within a
network of small throats retain oil).
England et al. (1987) carried out experiments with sandstone carriers of
various porosities to investigate the conditions for an interconnected oil col-
umn through the pore network and the necessary saturation for an oil
breakthrough (Table 7.6). Based on their results 50% of the pore volume must
be petroleum-saturated for flow of petroleum to occur. Although their sa-
turation values for breakthrough tend to increase from 20 to 90% with de-
creasing porosity (from 20 to 4%), data variation is such strong that for many
carrier rocks a general mean value of 50% is too imprecise for a prospect
evaluation. A 50% saturation may be necessary for lower porosity rocks with a
unimodal pore size distribution (Fig. 7.27c). Other types of rocks with bi- or
polymodal distribution functions bear the chance for much lower saturation
values (Fig. 7.27a,b). For better approximations (if experimental data are
lacking) it is therefore suggested to estimate the necessary saturation for
carrier bed migration from the geometry of the pore size distribution in
analogy to the geometric calculation of displacement pressure in reservoir
rocks (Fig. 7.27).The inflection point of the first pore size modality with the
largest pore size provides the minimum saturation and the smallest pore size of
the same modality gives the maximum saturation at which fluid flow is gen-
erally obtained. In this way, carrier beds with a bi- or polymodal pore size
distribution may often provide very good drainage conditions because they
need comparatively few channels to the reservoir and only low saturation
values. Therefore they exhibit also low residual oil saturations.
A microscopic view (cryo-SEM photomicrograph) from a meandering mi-
gration channel within a sandstone after a core-flodding experiment (water-oil-
water) is given in Fig. 7.28 (Mann et al. 1994a). The residual oil phase occupies
predominantly the concave (sag pores) and convex curvatures along the pore
walls in contrast to the zones in between or like the smooth surfaces of well-
crystallised quartz which is only sparsely covered (Fig. 7.28a). A detailed view
of on one single quartz crystal provides the actual wetting conditions: quartz is
wetted by a 3-to 6-flm thick brine which is coated again by a 1- to 1.5-flm-thick
464 U. Mann et al.
oil film. Regarding the pore network at a somewhat larger scale means to
consider also the fabric of the sedimentary rock.
In typical water-wet oil/water systems, the amount of trapped oil can vary due
to the fabric of the sedimentary rock. Ringrose and Corbett {1994} compared
by numerical simulations the effective flow behaviour of two immiscible fluids
in a variety of heterogeneous sandstones. For typical subsurface flow rates and
patterns of rock heterogeneity in hydrocarbon reservoirs, capillary forces can
result in significant amounts of residual oil {trapped due to the bypassing of
the non-wetting phase. Ringrose and Corbett (1994) investigated the effects of
uniform versus crossbedding and graded bedding, faulted layers versus parallel
layering, and horizontal versus vertical flow in wavy bedded sandstones on
relative oil permeability {Fig. 7.29}. They found values between about 40% and
65% of residual oil trapped due to the type of heterogeneity.
The effects of small scale heterogeneities must be upscaled when large-scale
flow behaviour - as in a sedimentary basin - is assessed from numerical or
experimental simulations at the core scale level. Corbett et al. (1992) scale up
their generalised flow models in a number of stages dictated by the respective
sequence stratigraphic framework.
Interfacial tension between oil and water and the contact angle between the oil!
water and water/pore wall contacts are parts of the Young-Laplace equation.
They vary according to petroleum composition and the salts dissolved in the
brine. Water-wet conditions prevail in most reservoirs, but oil-wet and mixed-
wet systems also occur. The type of wetting has considerable influence on both
the capillary pressure and the relative permeability {McDougall and Sorbie
1992}, and thus also on residual oil saturations.
The exact composition of the migrating petroleum phase is generally un-
known, and an important parameter, the gas content, can hardly be assessed.
Already during expulsion of the oil phase from the source to the carrier rock,
gas losses by diffusion are the rule, and significant amounts of gas losses may
be involved. However, it is unclear what magnitude oflosses must be taken into
account. As another consequence, fluid properties such as viscosity, interfacial
tension and individual wetting characteristics which together affect the relative
permeability and losses during migration, are difficult to estimate.
Fig. 7.27a-c. Pore radius equivalents versus pore volume (minimum petroleum saturation Sc
necessary for breakthrough are calculated according to pore volume value at first inflection
point; maximum saturation Sm estimated from calculated displacement pressure). a bimodal,
Sc = 15.2%, Sm 35.7%. b polymodal, Sc = 17.8%, Sm 37.0%. c unimodal, Sc = 53.8%, Sm 73.3%
Petroleum Migration: Mechanisms, Pathways, Efficiencies and Numerical Simulations 465
70
A
C a
63
60
B
55
}()
.s
./0
35
30
25
10
15
10
A
45 b
3'
)0
25
20
I)
10
)0 A c
2.
26
24
22
20
11
16
14
12
10
Fig. 7.28a,b. Cryo-SEM migrograph of a migration channel from a core flooding experiment
(water-oil-water) with a Wealden sandstone. a Total view of meandering pore channel where
residual oil occupies predominantly the concave (sag pores) and convex curvatures of the
pore walls in contrast to the zones in between and the smooth surfaces of quartz crystalls
which are only sparsly covered. b Detail from a showing wetting conditions. The quartz crystal
is wetted by a 3-6 11m thick film of brine which again is coated by a 1- to 1.5-llm-thick oil film.
(Mann et al. 1994a)
1.0 1 - - -- -- - _ _ _ __ _---.
Graded bedding
0.8
2 m model
0.6 5 em grideclls
50 to 500 mD layers
~r-------4
0.4
0 .2
a 0.0 +-~.,.-~.,....~-,-~_,_~...,.c~~~_...~--.j
0.0 0.1 Q2 Q3 OA Q5 0.6 0.7 0.8
Water saturation
1.0,-------------------.
~
:.c
~
'0
~"
.:::"
;;
-;;
0.8
0.6
0.4
11 20em model
2 mmgrideell
50 to 500 mD laycrs
5 mD fau lts with
'" 0 .2
< Ie m throw
b 0 .0 +-~..---~y--.--,,--.-.-.::!!!~-..-:~,-_~_l
0.0 0. 1 0.2 0 .3 0.4 0.5 0.6 07 0.8
Water Saturation
1.0 r-----q;,------- - -- - - - .
Way bedded
.. . .. . .
.'';''''~~
;- .~
~ 0 .8
~- .~
:.c
" :~~~
~ 0.6
co.
'0
5 m model
.~ 0.4 5cm gridcells
;:;
-.:; 30 to 1300 mD layer
'" 0.2
c 0.0 +-.....-,.-~.---.--,.-....-.__.;:::!~I;=I~~~.__J
0.0 0.1 0.2 0.3 0.4 0 .5 0.6 0.7 0.8
Fig. 7.29a-c. Relative oil permeabilities for different types of sedimentary fabrics of sand-
stones. The amount of trapped oil is given by lOO% water saturation when the relative
permeability approaches zero. a Uniform bedding versus cross-bedding and graded bedding.
b Parallel layering versus faulted layers. c Horizontal versus vertical flow in wavy bedded
sediments. (Ringrose and Corbett 1994, with kind permission of the Geological Society,
London)
468 U. Mann et al.
7.5
Simulation of Migration Processes: The Geological Framework
7.5.1
Prerequisite: Extension of the Conceptual Model for Migration Modelling
User Awareness
and ensure that sufficient support and training is provided by more experi-
enced users or software vendors - a crucial factor when constructing con-
ceptual models for petroleum migration modelling.
7.5.2
Conceptual Model: Migration System and Pathways
7.5.3
General Numerical Model
The dominant transport mechanism of petroleum, i.e. oil and gas, strongly
depends on its physical and chemical properties and the type of carrier rock. In
most carrier-reservoir rock systems, separate phase hydrocarbon migration is
the most important process. In this case, liquid petroleum with variable pro-
portions of dissolved gas or gas with variable proportions of high-molecular-
weight hydrocarbons is transported as separate phase in the otherwise water-
saturated pore space. Buoyancy is the decisive factor controlling the direction
of this transport.
Petroleum transport as a diffusion process in aqueous solutions in mole-
cular or micellar form is of lesser importance for the migration process. Ex-
ceptions may be organic-matter-Iean source rocks, in which insufficient
petroleum is generated to allow separate phase transport. Certainly, diffusion is
more important for low-molecular-weight hydrocarbons, i.e. gas, than for
high-molecular-weight hydrocarbons due to the greater solubilities of the
former. Both mechanisms - separate phase flow and the diffusion of low
molecular hydrocarbons in aqueous solutions - are included in the model
presented here.
The usual method for the description of separate phase flow and diffusion
processes on a macroscopic or basin scale is the continuum approach. The
object or region of interest is assumed to consist of uninterrupted volume
elements and every field value (temperature, pressure, saturation, concentra-
tion) and every material parameter (permeability, thermal conductivity) is well
defined in the volume element as a single, effective or average value. Fur-
thermore, the value can vary continuously from element to element at least for
parts of the system. This method requires that the size of the volume element
must be small compared to the system being modelled (basin scale) but at the
same time large compared to the structure elements (pores). Scale sizes used in
basin modelling are shown in Table 7.7.
In the continuum approach information on the amount and composition of
each fluid phase is required for each volume element (Fig. 7.30). In the model
the fluid phases - a liquid aqueous phase, a liquid petroleum (oil) phase and a
gaseous phase - can fill the pore space between the solid material matrix
formed by lithological and organic particles. The three different fluids are
treated as insoluble fluid phases in the flow module. Therefore, the presence of
well-defined interfaces between the three fluid phases can be assumed. Ad-
ditionally, every phase consists of several compounds (Fig. 7.30) and the
fractions of all of these defined compounds are calculated and stored for each
volume element. Furthermore, the methane content of the aqueous phase is
important for the reservoir diffusion model, and the subdivision of the liquid
472 U. Mann et aI.
Molecular scale
.. pore space
mineral 0\11
matrix water free
methane
oil2
kerogen
: dissolved
cement methane oil3 nitrogen
Fig. 7.30. Phases and compounds of the volume elements and cells
Petroleum Migration: Mechanisms, Pathways, Efficiencies and Numerical Simulations 473
geometric average: c = c
s (1-'1') a~Sa
.c +c o~So
.c
g.Sg
with c = effective cell value, <I> = porosity, Si = saturation of the fluid phase I
(a = water, 0 = oil, g = gas), c = value of the phase i (a = water, 0 = oil,
1
g = gas).
During the history of sedimentary basins that can evolve over time spans of
several ten to hundreds of million years, changes in the rock and fluid com-
positions occur. The fluid carrier rocks experience large changes through time
due to geometric (tectonic and compaction) processes or changes in their
properties due to changing temperature and pressure conditions. Then the
properties of the fluids themselves change, for example, due to chemical
cracking of the petroleum. A dynamic analysis of the petroleum system is
therefore meaningful only with an accurate and complex basin analysis, and
the petroleum migration models must be embedded in the reconstruction of
the thermal and pressure history of sedimentary basins. A well-calibrated
thermal analysis is of immense importance for several aspects of the petroleum
migration models, especially for the calculation of the petroleum generation
rates and for the determination of fluid properties such as viscosities and
diffusion constants. Thermal markers such as vitrinite reflectance, illite crys-
tallinity and specific biomarker ratios are used to calibrate the geological and
geothermal history. An overview of the main modules of a complete basin
simulation is given in Fig. 7.31 (see Chap. 2 for the details of thermal mod-
elling).
Primary Migration
The factors that are important for the expulsion process from source rocks
differ from those that control further migration in carrier or reservoir rocks.
For example, the saturation values that control initial expulsion from source
rocks in separate phases are generally assumed to be higher than those used for
initial movement through carrier rocks. The most common approach at pre-
sent is the use of specific saturation threshold values for different source rock
types. Typical bulk values for cells with sizes ranging from several tens of
meters to 500 m, are 2-5%.
However, more complex expulsion models that take the various mechan-
isms of the petroleum generation process into account are also employed. In
these models the beginning of petroleum expulsion is related to the controlling
physical properties and processes, instead of assumed threshold values. The
474 U. Mann et al.
Deposition, Erosion
construction of the new geometry and
the finite element mesh
4. Petroleum Expulsion
- separate phase flow and fracturing
5. Petroleum Migration
- separate phase flow and diffusion
complex expulsion model used here in addition to the above threshold sa-
turation concept is described by Diippenbecker (1990) and Diippenbecker and
Welte (1992) and was calibrated for a specific source rock in northern Ger-
many.
The model is based on analysis of the densities of kerogen and petroleum
during kerogen cracking. Kerogen has a significantly higher density than
petroleum and the densities of both vary with increasing transformation, as
shown in Fig. 7.32 for a typical petroleum generation system. A potential vo-
lume increase occurs when petroleum (oil or gas) is generated in source rocks.
With the assumption of isobar conditions this additional volume is propor-
tional to the area between the two specific volume curves as shown in Fig. 7.32.
Petroleum Migration: Mechanisms, Pathways, Efficiencies and Numerical Simulations 475
2.0
1.5
0.5
kerogen
Fig. 7.32. Kerogen and petroleum specific volume changes during oil generation
Due to the limited pore volume, this potential volume increase cannot oc-
cur, and the potential increase in the volume of the material is instead trans-
ferred to a marked increase in the petroleum phase pore pressure. Several state
equations (pressure-volume-temperature curves) for the water and the petro-
leum phase are used to describe this pressure increase. Of special significance
is the role of the different pore classes (pore size distributions) and the
amounts of adsorption that are considered in detail. The pore pressure increase
allows the formulation of an expulsion condition. As a common concept in the
continuum approach the corresponding field parameter is compared to a
constant material parameter resistance, which acts against the effect. In the
model presented here, two expulsion mechanisms are considered.
One process is separate phase flow through the pore system. The field
parameter is the petroleum phase potential (difference of real pore pressure
and hydrostatic pressure), while the capillary pressure acts as the resistant
material parameter. Expulsion therefore occurs as separate phase flow through
the pore system when the petroleum potential exceeds the capillary pressure of
the material.
The second process is separate phase flow along fractures. Microfractures
exist in most fine-grained rocks and are partly a product of the volume ex-
pansion of the organic matter during petroleum generation (Littke et al. 1988).
The stress intensity factor describes the stress extension at the crack tips and is
the driving force for fracture extension. This field parameter can be calculated
from the pore pressure increase with the help of mechanical laws that define
476 U. Mann et al.
Secondary Migration
Several mechanisms such as separate phase flow, diffusion, solution and dis-
solution of gas in oil and water and chemical cracking simultaneously influence
and define the complex process of secondary migration. Due to this multi-
processing behaviour the simulation technique must also consist of multiple
models. Each model acts independently within the predefined volume elements
(see Fig. 7.30) and causes changes in the composition of the phases and
compounds. In this way the tracing of petroleum from different source rocks
can be realised side by side within the same volume element. Mathematically
the models are mainly formulated as boundary value problems of second-order
differential equation systems or they are described in terms of additional op-
erations, equations or conditions.
7.5.4
Specific Items of the Numerical Model
must be noted that this approximation is not suitable if the different fluid
phases have strong interactions during the flow process. Thus the adaptation of
Darcy's law for multiphases has the following form:
f k ij . kf f
v·1 =---·a·u
vf J
permeability
in log ( mD )
6
2
limestone
-0 siltstont:
shale
-2
-4
for basement . . all . granite. basalt
permeability = I O· I~ Ill))
-6
o ... depo. itional conditions
o 10 20 30 40 50 60 porosity in %
Some typical relative permeability curves are shown in Figs.7.34 and 7.35
(after Aziz and Settari 1985). Water is considered to be a wetting phase to both
oil and gas, gas is considered to be the nonwetting phase to both water and oil,
and oil is considered to be the nonwetting phase to water and the wetting phase
to gas. The relative permeability functions (linear or quadratic) of water and
gas are assumed to be a function of the water and the gas saturation respec-
tively. The relative permeability of oil is assumed to be a function of both, the
water and the gas saturation and it is calculated as follows.
krw = f(SW) kro = f(SW, sg) krg = f(Sg)
krg max
,
--------------------------~------.
o
o swini swmax
The fluid potential (or overpressure of the fluid) is derived from the real
pore pressure field under consideration of the buoyancy potential:
8i (pfV[) + Sf8t (pfcp) + cp8t (pfSf) = _cp8t (pfSadd) (f: water, oil, gas)
with <I> = porosity, Sf = fluid saturation, Sadd = additional saturation due to oil
and gas generation. The first two terms of the equation are well-known flow
terms from general fluid mechanics, while the other two represent special basin
modelling effects. These effects are compaction (porosity change) and petro-
leum generation (fluid sources).
The porosity change is caused by the changing overburden load potential
due to subsequent sedimentation. This is described by the following com-
paction law:
8t cp = -(1 - cp) . C· at(ua - uf)
with C = compressibility, ua = potential of the overburden material, and
uf = fluid potential. The difference of the overburden and the fluid potential is
the effective stress. The sedimentation rate directly affects the overburden po-
tential. Therefore both overpressuring and compaction processes are strongly
influenced by sedimentation rates. Compressibility values, used in the model,
are shown in Fig. 7.36 for the main lithology types (after Wygrala 1989).
The source term for petroleum generation contains the additional or gen-
erated petroleum (oil or gas) saturation. The representative values for the
petroleum kinetics are the chemical petroleum potentials (mass of hydro-
compre sibility
in log ( MPa' \ )
2
coal
shale
o
siltstone
-I marl
sandslOne
-2
-4
o ... depositional condition
o 10 20 30 40 50 60 porosity in %
carbons per Toe mass} and the relationship between the chemical potentials
and the generated saturations are the following:
Petroleum Generation
Ker] ------+
k12 0'1 k32 0'1 k22 Gas
1 Ker] ------+ Gas 1 ] ------+
m ]
OtZ = (r Lk2jYj) + (Lk3jXj) for gas
j=] j=]
Petroleum Migration: Mechanisms, Pathways, Efficiencies and Numerical Simulations 483
xlO 55.5
(% HI)
Kerogen Type II
SO
Kerogen Cracking:
HI = 492 mgHC/gTOC
40 A = 2.865xlO27 Ma-I
29.3
30 Oil- Cracking:
E= 57 kcallmol
A = 9.467x 1027 Ma- I
20 f= 0.45
10
0
40 SO 60 70 E (kcaVmol)
Fig. 7.37. Kinetic parameters of kerogen type II. (Tissot, in Waples et al. 1992)
Xin
30 Oil- Cracking:
E= 62 kcal/mol
A= 1.736 xl0 28 Ma-I
20 f= 0.55
10
0
40 50 60 70 E (kcallmol)
Fig. 7.38. Kinetic parameters of kerogen type III. (Tissot, in Waples et al. 1992)
484 U. Mann et al.
Thus, r = l~ = 0.57
If the presence of different oil components is considered, the distribution (Xi
of the mass ratios of these components must be given for the kerogen~oil
reaction to decide which amounts of the different oil components are produced
from the kerogen.
The petroleum kinetics described above can also be used to describe the
reactions of different hydrocarbon component classes (for example Cl, C2-C4,
CS-C6, C7 -C 15, C 15+ ). Then instead of the properties of a whole kerogen type,
only the properties of the special hydrocarbon component class must be en-
tered in the kerogen reactions. After the model has been processed with several
component class kinetics, an overview over the distributions of the hydro-
carbon classes can be obtained.
The kinetic approach indicates that the conversion of kerogen to oil and gas
is more strongly effected by temperature (exponential influence) than by time
(linear influence). For oil and gas generation calculations the use of the actual
kinetic equations requires numerical integration due to the complexity of
thermal histories. It should be emphasised that the extrapolation of kinetic
processes from laboratory experiments into geological time is still a problem
which can be controlled only by calibrating with precise temperature histories
and real cases.
In a multiple source rock concept the petroleum from each different source
unit is tracked or traced separately throughout its entire migration history to
ensure that the properties of mixed petroleums are determined correctly. It is
therefore always possible to see how much of the petroleum in a specific cell
comes from which source unit (see Fig. 7.39).
CarrierlReservoir Cell
Access to
- Masses and Volumes of Oi I A, Oil B, GasA, GasB
- Phase and Bulk Values are Arithmetical or
Geometrical Averages of the Compound Values
i
Cell of Source Type B
Definition of
Cell of Source Type A - TOC and HI Values
Definition of - Kerogen B Kinetics
- TOC and HI Values - Properties of Oil B and Gas B
- Kerogen A Kinetics
- Properties of Oil A and Gas A
draulic fracturing conditions can also be defined. When one fracture condition
is satisfied during a time step, then the permeability value of the considered
element is increased by several orders of magnitude. The following fracture
conditions can be applied: (a) the excess hydraulic pressure exceeds a certain
proportion of the lithostatic pressure (generally in the range of 0.6 - 0.8); (b)
the real pore pressure exceeds a threshold pressure value. The increase in
permeabilities is calculated on a logarithmic scale:
.1lgk = f . pe - pc
pc
where f denotes the factor of permeability increase, pe denotes the real (pore or
over-)pressure, and pc is the corresponding threshold pressure.
The cementation/dissolution condition is formulated in terms of a critical
depth or temperature, or a specific geological age for a certain layer. If this
condition is satisfied, the porosity of the volume cell is increased or decreased
by the cementation volume. Because of the strong dependency of the perme-
ability on the porosity values the permeabilities also change significantly. The
bulk material parameters such as thermal conductivity, heat capacity and
density are effected by the solid cement properties. Some typical cement
properties are listed in Table 7.8. Especially the considerable effect on the
permeability values necessitated the implementation of both processes, ce-
mentation/dissolution and fracturing in the fluid flow simulation.
Fault Model
As faults can have very different and complex effects on fluid transport pro-
cesses, their effects are handled by a variety of models. They can, for example,
486 U. Mann et al.
Salt Tectonics
Petroleum reservoirs and salt layers and domes are often closely associated as
salt can act as an ideal caprock due to its very low permeability. Moreover, salt
layers affect both the temperature and pore pressure fields, due to their ex-
tremely high thermal conductivities (4.5-6 W m- I K- I ) and their low perme-
abilities and compressibilities. The volumetric modelling of salt layers through
geological time is therefore of great importance in basin modelling.
As a reaction to overburden load (depositional mass), salt layers tend to
build domes, sometimes of up to several kilometres thickness (Fig. 7.41).
During this doming the salt layer behaves as a viscous fluid. A relatively simple
model that includes the description of the geometric changes on the basin scale
Petroleum Migration: Mechanisms, Pathways, Efficiencies and Numerical Simulations 487
Fault Element
Material Tensor
Diffusion
taken into account. First, the quality of the dissolved hydrocarbons is con-
trolled by the concrete field values (temperatures, pressures) and in the case of
nonequilibrium the hydrocarbon compounds must be dissolved in or exsolved
from the pore water. Secondly the diffusion fluxes are calculated and realised
along hydrocarbon concentration gradients.
The solubility of light hydrocarbons in water is usually described as a
function of temperature, pressure and salinity conditions as state diagrams or
state laws. In Fig. 7.43 the methane solubility (in ppm) is calculated after Haas
(1987). Additionally, typical pressure and temperature intervals of reservoirs at
2, 4 and 6 km depth are shown.
The solubility is the highest possible concentration under the given field
parameters; the concentration depends on the available amount in the free gas
phase. In every time step the free gas phases and the laws of solubility are
analysed to determine the solution and dissolution process that determines the
aqueous hydrocarbon concentration field. This concentration field is the basis
for the calculation of the diffusion fluxes by using Fick's law applied to the
porous media (see KrooB et al. 1992a,b).
J = -¢ . Deff . grad(C W )
with <I> = porosity, Deff = effective diffusion coefficient, CW = concentration of
the HC compound in water. The diffusion coefficient strongly depends on
temperature. This is realised by applying the following Arrhenius-type law:
D( T) [E (1T- 1)]
= D150 . exp -R:. 423.15 with R = 8.314 J/mol/K
and E = 50 kJ/mol
Here D(T) denotes the diffusion coefficient at temperature T (in K), D1SO is the
effective diffusion coefficient at 150 DC, (423.15 K), E is the activation energy
and R the gas constant.
A typical scenario is described in Fig. 7.44. When gas is generated in the
source rock, first the water phase must be saturated with methane until the
maximum solubility for methane is reached. Then methane can also form a free
phase and move as separate phase transport. Therefore, in most of the section
Petroleum Migration: Mechanisms, Pathways, Efficiencies and Numerical Simulations 489
80
pore
pressure
for solubility values of
in
500 ppm ... 10000 ppm
MPa
60
regions of typical
reservoirs
40
20
ti I~
top
seal ~ u
reservoir
'W~OI saturated water I
I~
carrier phase
A.
seal \U
\ I
lft
reservoir
carrier
source
\
bottom
the water phase is saturated with methane and thus diffusion is a relatively
small but continuous and basinwide process.
7.5.5
Case Histories
Introduction
Basin evolution of the Styrian Basin can be subdivided into an early Miocene
synrift and a middle to late Miocene postrift phase of subsidence. As pre-
sented in detail in Chapter 2, the heat flow history of the basin is governed
primarily by Miocene (Karpatian to early Badenian) volcanism. Volcanic
centres were characterised by extremely elevated heat flows (> 300 mW/m2 )
and heat flow decreased to background values (about 120 mW/m) at a dis-
tance of about 10 km. A second volcanic phase producing basalts in Plio-/
Pleistocene times had only minor influence on the regional heat flow pattern.
The basin is 100 km long, 60 km wide and more than 4 km deep and is
located at the eastern margin of the Alps, forming part of the Pannonian Basin
System (Fig. 7.45). Many subbasins of the Pannonian realm contain prolific
hydrocarbon deposits. However, in the Styrian Basin no commercial hydro-
carbon accumulations have been detected to date. Only a small subeconomic
gas deposit was encountered in middle-Badenian algal reefs near the northern
margin of the basin in the Ludersdorf area ("L" in Fig. 7.45).
A recent paper evaluates the hydrocarbon potential of the basin using or-
ganic geochemical and numeric modelling techniques (Sachsenhofer, 1994).
For this purpose the above heat flow model, based upon extensively calibrated
temperature histories along two cross sections (I, II; Fig. 7.45) and for five
individual wells was established (see Chap. 2). This heat flow model and or-
ganic geochemical data were used to reconstruct hydrocarbon generation and
migration along a third cross section (III; Fig. 7.46). The most important re-
sults are: (a) mature oil- and gas-prone source rocks exist in the lower Miocene
section (Ottnangian and Karpatian levels); (b) hydrocarbons in close vicinity of
Miocene volcanoes may be lost to the surface because no seals were deposited
at the time of generation (Karpatian and early Badenian); (c) the area around
cross section III has a good hydrocarbon potential, because of relatively late
generation. Because of the great impact of the time factor on the hydrocarbon
potential quantitative models of hydrocarbon generation and migration along
cross section III are presented in this contribution.
...,
...,
eli ,.,
e8 ~
CI)
...
~
"
q,
v
q. "
10 km
•
N
I
Plio-/Pleistocene
volcanic rocks
Fig. 7.45. Position of the Styrian Basin within the Alpine-Carpathian-Pannonian region and
sketch map of the Styrian Basin with location of volcanic rocks (Sachsenhofer, 1994). The heat
flow model for the Styrian Basin (Fig. 7.49) was calibrated along cross sections I and II.
Numeric modelling of hydrocarbon migration is performed along cross section III. A sub-
economic gas deposit was detected in the Ludersdorf-Wollsdorf region. Li, Litzelsdorf 1; S,
Stegersbach 1; Wa, Waltersdorf 1; BI, Blumau 1, la; F, Fiirstenfeld 1; U, Ubersbach 1; B,
Binderberg 1; J, Jennersdorf 1; W, Walkerdorf 1; Wo, Wollsdorf 1; L, Ludersdorf 2; M, Mit-
terlabill 1; N, St. Nikolai 1, 2; P, Perbersdorf 1; Pi, Pichla 1; Mu, Mureck 1
shallow northern part the section contains middle Badenian algal reefs, which
host the only significant gas accumulation in the Styrian Basin known today.
The basin fill reaches a thickness of 4000 m at the southern end of the transect.
The geological evolution of the cross section was defined by a total of 19
gridpoints including two shallow wells in its northern part and 28 geological
events (Fig. 7.46):
- Ottnangian (events 3-4): Non-marine (vitrinite- and alginite-rich) source
rocks were deposited along the southern part of the transect.
492 U. Mann et al.
N s
Wo l L2 GP17
5 10 15 km
Fig. 7.46. Stratigraphy along cross section III. Potential source rocks occur in Karpatian
(basinal facies; vertical hatching) and in Ottnangian levels; potential carrier rocks occur in
post-Karpatian sediments. The only (subeconomic) gas deposit in the Styrian Basin was found
in middle Badenian algal reefs in the Ludersdorf area. For well names see Fig. 7.45; GP17,
gridpoint 17
Table 7.9. Key parameters of potential source rocks in the Styrian Basin (the generative
potential is described using the nomenclature of Peters 1986)
Generative potential
Non-marine Ottnangian
and Karpatian
Coaly samples 0.35-6.5 30-160 Fair
Alginite-rich samples 6.0-8.0 325-450 Very good
Marine Karpatian
Basinal facies 0.5-l.3 350-400a Fair
Deltaic facies 0.2-1.5 30-80 Poor-Fair
Table 7.10. Source rock and petroleum parameters used for modelling of hydrocarbon gen-
eration and migration in the Styrian Basin
Migrating petroleum type: "high viscous gas". (Reason: gas was found in Ludersdorf and
condensates occur in several other wells). Primary migration: saturation model. Boundary
conditions: open basin sides.
aTo be conservative, a relatively low TOC content is assumed for non-marine samples
bKinetic parameters of Brent coal are used, because most samples contain type III
kerogen and the kinetic parameters are similar to those for alginite-rich samples
ments, developed along the northern part of the cross section. These sedi-
ments were buried by shaly and marly sediments in late Badenian times.
Early Badenian conglomerates and sandstones and middle Badenian algal
reef limestones are potential reservoir rocks.
- Sarmatian (events 17-20): Sarmatian sediments were deposited in a sea with
reduced salinity. Normal fault tectonics along the northern margin caused
the formation of the horst-structure in the Ludersdorf area (L2 in Fig. 7.46)
during Sarmatian times.
- Pannonian and Pontian (events 21-23): Marine conditions were replaced by
limnic and fluvial conditions with deposition of intercalations of shaly and
sandy sediments.
- Pliocene and Quaternary (events 24-28): Uplift started in Pliocene times and
resulted in erosion of 260-340 m of sediment.
There are only few calibration data along the studied cross section. However,
according to the well-calibrated heat flow model presented in Fig. 7.47 the
following heat flow model is considered as the most probable one (heat flow
model "middle" in Fig. 7.47).
The influence of high Miocene heat flows around the volcanic centres was
restricted to a relatively narrow halo. It is therefore thought that the area of
cross section III, which is located more than 10 km from the next volcanic
centre, was not influenced by extremely raised heat flows during Karpatian and
Badenian times. An Ottnangian to middle Badenian heat flow of 120 mW/m2
seems reasonable. Probably heat flows decreased afterwards until the end of the
middle Miocene, when they reached their present values. Present heat flow
along the northern end of the transect is about 75 mW/m2 and decreases
toward the central and southern part to 63 mW/m2.
494 U. Mann et al.
§
·
10 · Panno n.
<l>
• C
<l>
0 Sa rmatiar
• 0 <l>
L.- §
~~
--
·c
15
:;: M. - ~
0
I
'"'
--
E.-
· Ka rootia n
Ottna na .
£ r---
· 0
w Eggen-
20 b urg lo n
,.\ ,
I
.~ Roman. .\
, \
, I I
,,
I
5 a::: Dazlon
1\
, I I
"" ~ , 1-'-
, -,,- I
,
Pontion
.," ,
--,-,- \ ,
- '- I
- -'I
, ,
'0 - I
,
I
~ I
,
,I
,I ,
I I
I
, I I
15
V
a::: Dazion , I
, ,
5 ,I
,
Pontian 'I
, , ,
I
,
(J) 2
, ,
c .9 ,
I
, ,
,, ,
10 (J) Pomon. , ,
~.-- ,,
, I ,
"" , , ,
~
I
,'
I
, I
, ,/ D; ;-~
,>
I
.' V
IF--
L Lr
Fig. 7.48a,b. Calculated temperature, vitrinite reflectance, oil and gas generation histories for
three lower Miocene levels of gridpoint 17 (GP17), cross section III. a Heat flow scenario
"middle". b Heat flow scenario "hot" (petroleum potential of the Ottnangian layer was cal-
culated using kinetic data of type III kerogen (Espitalie et al. 1988), petroleum potential of
Karpatian layers was calculated using kinetic data of the Karpatian basinal facies
496 U. Mann et al.
N s
Wol L2 GP17
3 - Direction of migration
Early Badenlan (15.2 mybp)
4~--~------~--~~~--------------~
k.j=~~~~~~~~~
2
Hydrocarbon soturotlon
3 20 - 80 %
• >80%
4 Middle Badenlan (14.0 mybp)
3
Early Sormotlon (12.4 mybp)
4 ~------~--------~--------~----~
o 5 10 15km
Fig. 7.49. Petroleum saturation and migration along cross section III for middle Miocene and
present times. Isolines show excess pressure (MPa)
kmr----------------~==------------,
3
la1e Sorma1ian (11 9 mybp)
4 ~--------------------------------~
2 Basement
3
present
4 +---------~------__~------_T--~~~
a 5 10 15km
D Ottnangian D Korpatian D Badenian
D Sarmatian D Pannonian
OJ
Heat flow (mW/m2) Mass-% of initia l H C-p otential
mybp 50 100 150 10 2 0 30 40
O~~r---+---~~--~--+---~~r-~--~--~r----I
.Q,1 PIe·sloc.
a.. - -"m iddle"
~ Pliocene
"
5 0::
Pentlon Carrier
O>t---t
Loss to surface
O>§
10 C Pennon.
0>
0-1-:----1
o 0> Sarma!.
-- c
~ ~ L.- _g
15 ~ M .-
£
Q)
E.-
~ Eggen-
20 burgla n
b)
Heat flow (mW/m2) Mass·% of initial HC-potentia l
mybp 50 100 150 10 20 30 40
o a)
Pleistoc.
0::
- 'hot"
H Pliocene
5 0::
"
Pon~an
O>t-- - t
0>15 Loss to surface
10 C --' Pennon.
0>
() -1-:----1
o Q) Sarma!.
:;;; '0
l.. §
c
15
""'-0
~ M.· g
E.· '"
20
Sensitivity Analysis
In the framework of a sensitivity analysis the heat flow history along the
transect was modified, accounting for a "hot" scenario (Fig. 7.48), which
considers the highest geological meaningful Miocene heat flow. This value is
derived from the Walkersdorf 1 well; "w" in Fig. 7.45 where heat flow did not
exceed 170 mW1m2, although the well is situated close to a volcanic centre.
The calculated temperature and maturation histories at gridpoint 17 differ
significantly from the original scenario. Higher Karpatian and early Badenian
temperatures result in an early generation phase, which ended already during
the early middle Badenian and in a higher gas/oil ratio (Fig. 7.48). Only small
amounts of hydrocarbons were generated after the early Badenian.
Although the general migration pattern is similar to the original scenario,
the quantification of hydrocarbon generation and accumulation shows sig-
nificant differences (Fig. 7.50). Because of higher late Karpatian and early
Badenian temperatures more hydrocarbons were generated (about 48% of the
primary potential). However, most hydrocarbons were lost to the surface in
early Badenian time. Because of the weak post-early Badenian generation only
about 10% of the primary hydrocarbon potential was accumulated in carrier
rocks. The pressure build-up by the relatively small amount of accumulated
hydrocarbons did not result in a Sarmatian break-through through the middle
Badenian seal. Therefore, and in contrast to the original scenario, no hydro-
carbons were lost to the surface during the Sarmatian. Again some hydro-
carbons were lost since the Pliocene along the northern basin side.
Conclusions
The heat flow evolution and the time-relation between hydrocarbon generation
and trap formation have an important effect on the hydrocarbon potential of
the Styrian Basin. The elevated heat flow in close vicinity of Miocene volcanoes
resulted in an early (Karpatian to early Badenian) petroleum generation phase
near the volcanoes. Because no traps were formed at that time, the generated
hydrocarbons will have been lost. Hydrocarbons generated along cross section
III had a chance to become trapped and form accumulations. The calculated
amount of accumulated hydrocarbons depends on the applied heat flow his-
tory. Although more hydrocarbons are generated in the hot scenario, only
small deposits evolve and most hydrocarbons are lost to the surface. In the case
of the scenario "middle", which is considered as the most probable one, more
hydrocarbons are trapped. This is above all a consequence of the relatively late
500 U. Mann et al.
generation phase. Because of higher early Badenian temperatures and the loss
of early generated oil during early Badenian times, a more realistic higher gas/
oil ratio is calculated for the Ludersdorf deposit in the "hot" scenario.
Geological Setting
The geological evolution of the Northwest German Basin, the burial history of
Carboniferous source rocks and the heat flow history within the study area is
summarised according to the following five principal stages.
- Stage 1: Deposition of thick coal-bearing strata occurred during the late
Namurian and early Westphalian. These units are the source rocks for most
of the gas in the Northwest German Basin. Also, some commercial gas fields
exist in Carboniferous sandstones.
- Stage 2: After a short period of erosion, deposition of volcano clastics {o-
600 m} occurred during the Lower Permian {Autunian}. This time of en-
hanced heat flows represents also the first gas generation from the Carbo-
niferous strata. It is followed by fluvio-deltaic sedimentation during the
Saxonian. This upper part of the Lower Permian "Rotliegend" series con-
tains the most prolific reservoir sandstones of the area.
- Stage 3: Marine evaporite sequences characterise the following Upper Per-
mian {"Zechstein"} which serves as the major regional seal.
- Stage 4: During the Triassic and Jurassic, the depositional environment
fluctuates between shallow marine and continental. This period represents
the second phase of gas generation in the Carboniferous and is also the time
of the beginning doming of Zechstein salts, which caused the formation of
many important gas traps. Reservoir rocks occur in the Lower Triassic,
whereas the overlying formations are of limited significance with respect to
gas accumulation.
- Stage 5: After some erosion during Early Cretaceous times, sedimentation
continued and maximum depths were reached by all formations in the
Cenozoic. The Cenozoic is the third period of gas formation from the
Carboniferous source rocks.
The gases in the Lower Permian as well as in the Triassic and Carboniferous
reservoir sandstones are characterised by variable, commonly high, nitrogen
concentrations {<5 to >90%}. The nitrogen province in which Lower Permian
reservoirs contain less methane than molecular nitrogen is shown in Fig. 7.51.
As also shown in this figure, the high nitrogen concentrations occur in an area,
where the maturity at the top of the Carboniferous exceeds 3% vitrinite re-
flectance. Krooss et al. (1995), Krooss and Leythaeuser (1996) and Littke et al.
(1995) evaluated the coaly organic matter of the Carboniferous as possible
source for the molecular nitrogen in the region and concluded "that nitrogen
generation from organic matter is one, probably the most important, source
for nitrogen gas, provided that sufficient organic matter at high levels of ma-
Petroleum Migration: Mechanisms, Pathways, Efficiencies and Numerical Simulations 501
North Sea
Hannol'er
turation is attained" (Littke et al. 1995). In essence, coals generate upon ma-
turation about 20 times more methane than nitrogen, but the ratio of nitrogen
over methane increases with increasing maturation, and becomes greater than
one at maturity stages corresponding to vitrinite reflectance levels above 3%.
For applications in petroleum exploration the knowledge of this sequence of
events is useful only if it is possible to evaluate whether a given gas in a
reservoir accumulated during early or late generation phases. A prerequisite
for this reconstruction of the timing of gas accumulation is, however, the
knowledge of the temperature history of the source rock horizons and of the
related gas generation. These aspects are presented below. For the simulation
of the migration of both methane and molecular nitrogen the physical para-
meters described in chapter 2 (section 2.6.6) section xy for dry gas were used,
as well as the kinetics of methane and nitrogen generation from coaly organic
matter which is presented in the kinetics chapter (see Krooss and Leythaeuser
1996).
502 U. Mann et al.
Within the study area the first gas generation occurred during the early Per-
mian (Autunian) as discussed in the heat flow chapter. This first gas generation
from the Westphalian and Namurian source rocks was due to the volcanism
and high heat flow and happened despite the low burial depths of the coal-
bearing sequences. However, the present traps in the Saxonian and the major
Zechstein seals were not yet deposited. Therefore the model predicts that gas
accumulations could not persist and that the early gas generated during this
period was completely lost to the atmosphere (Figs. 7.52, 7.53). This first gas
was mainly methane, regardless of whether the Namurian or the Westphalian
are considered as effective source rock formations.
Much greater burial depths were reached during the Triassic and Jurassic,
representing the second phase of gas generation. The extent of gas generation
during this period depends to a great extent on the extent of gas generation
during the previous, early Permian gas generation period. Only in regions in
which the Permian heat flows remained on a "moderate" level will significant
gas generation have occurred from the Carboniferous source rocks
(Fig. 7.53A,B). Where, however, Autunian heat flows were very high, for ex-
ample, in the direct vicinity of volcanoes, the Triassic and Jurassic gas gen-
eration remained insignificantly small. This is assumed to be the case in the
northern part of the study area, where volcanic rocks reach a thickness of
600 m and more (Fig. 7.53C,D). The gas generated during the Triassic and
Jurassic was predominantly methane at all locations. Part of the present trap
structures were already available at that time, but due to the fact that salt
doming only started, another part of the traps was not yet constructed.
Furthermore, gas accumulations were possibly destroyed during the following
phase of uplift and erosion, which affected the basin in late Jurassic/early
Cretaceous times.
Greatest burial depths were reached during the Cenozoic which is accord-
ingly regarded as the third period of gas generation. The composition and total
volume of gas generated at that time strongly depends on the previous tem-
perature history of the Carboniferous source rocks: In areas in the south, where
the methane generation potential was not yet completed great amounts of
methane and only small amounts of nitrogen were generated (Fig. 7.52A,B). In
the north, in contrast, the methane generation from the source horizons was
already almost finished and mainly molecular nitrogen was generated
(Figs. 7.53C,D).
The gas composition of the individual reservoirs in the north and south of
the study area depends certainly not only on the gas charge from directly
underlying source rocks by purely vertical migration, but also on the lateral
migration within the most permeable rock types. According to the simulation
results, this lateral migration is generally directed from north to south at
present (Fig. 7.52B) with some exceptions. If this lateral migration had been
the dominant transport processes for the fluids in the subsurface, molecular
nitrogen generated in the kitchen area in the north would be expected to occur
in all reservoirs in high percentages. This scenario is, however, not predicted
"0
~
....
< U.IOO o
rn
c
0.1 3
1ftl!" ~i1tll.1g U I
lllOO J "--. ' ~"1~ If!) H'1t . A .. ~ ~ i1l'1t..M" ..4 ..... ~ - U a<;
s::,
- ....
~.
0.300 o
p.
0.400 s::
(t)
(')
0.51 ::r
0'
::;
n.GOO
en'
3
:!'
0.700 "0
0'
ET
(l.600
0.900 ~rn
~
(')
.. 1.000
'--I
'/UU" ~ ro'
1 ------.I ::;
~ (')
1 ro'
-~
18000 '"0'
::;
0..
1'000 Z
c
3(t)
....
;::;'
e!...
C/)
S'
E..
o·~
::;
'"
A V>
o\.;.>
Fig. 7.52A,B. Gas saturation and migration as simulated along a 200-km-long geological transect in northern Germany. A At the end of the Lower
Permian period which was characterized by high heat flows, B At present
_ _ _ _ _ _ _ _u_ -
1!\i1h 1"ot.\I Pelrulf!UIIi saturClllon o tTl II
---- V1
-I" " ~ o
0.\110 """
U.\
0.30
0.400
0.500
O_GOO
o.IOU
0.000
0.9
~ 1.000
~
s;::
B '"::;::;
~
!!'-
Fig.7.S2B
Methane Transf. Nitr. Transf.
Temp. (OC) Vitro ReO. (%) Ratio Ratio
o 100 200 300 0 2 3 4 5 0,0 0,2 0,4 0,6 0,8 0,00,20,40,60,8 1,0
30
60
90
! /
120
,-.,
150
e
~
a.> 180
e
E= 210
240
270
300
.../ f-
330
A
Fig. 7.53A-D. Evolution of temperature, vitrinite reflectance, methane generation and nitrogen
generation for the lowermost Westphalian and the Namurian at a site in the south of the study
area (A, B) and for a site further north (C, D)
30
60
) /
90
120
,-.,
150
e
~
~
e
a.> 180
I
I
E= 210
240
r
270
300
~ ..../ f.-I
330
B
Fig. 7.53B
Methane Transf. Nitr. Transf.
Temp. (0C) Vitro ReO. (%) Ratio Ratio
0 100 200 300 0 2 3 4 5 0,0 0,2 0,4 0,6 0,8 0,0 0,2 0,4 0,6 0,8 1,0
30
60
90
120
...e
,-.
150
'-'
180
e
Qi
E= 210
240
270
300
330
C
Fig.7.53C
30
60
90
120
...
,-.
e
150
'-'
180
e
Qi
E= 210
240
270
300
330
D
Fig.7.53D
Petroleum Migration: Mechanisms, Pathways, Efficiencies and Numerical Simulations 507
1000
2000
3000 ,,-...
E
'-"
4000 -5
(l,
11)
5000 0
6000
7000
~------------------------------------------------------~ 8000
nr------------~------------------------~~O
N, (CWA)
- - - C H . (C WAJ-_ _~ 10
20
N, (Namurian) -~~---_ _ _ -* 30
40
C H. (Namurran) 50
60
70
80
L------------------=========================~90
300 250 200 150 100 50 a
Time (million years)
Fig. 7.54. Dynamics of methane and nitrogen generation and expulsion since the Carboni-
ferous for one site situated in the south of the study area (A) and one site in the north (B).
Above, for each of the two sites the burial history since the Carboniferous (note the different
depth scales); below, the loss of initial gas generation potential (methane and molecular
nitrogen) for the lowermost Westphalian and the Namurian
1000
2000
3000
4000 E
'-'
5000 -5
Co
Q)
6000 Q
7000
6000
9000
~------------------------------______________________L 10000
~~~~--------------------------------------------r0
10
20
30
40
50
60
70
80
Fig.7.54B
and modelled gas compositions is achieved only if a loss of all pre-Cenozoic gas
from the basin (into the atmosphere) is assumed, and if only the latest, Cenozoic
gas fills the reservoirs. This scenario results in low predicted percentages of
molecular nitrogen in the southern reservoirs (about 5%) which closely fits to
data from nearby gas fields, and in high percentages of molecular nitrogen in
the north (> 50%), where real percentages of molecular nitrogen approach 90%.
A more nearly perfect fit would require a better knowledge of the masses of
organic matter in the deep-lying Palaeozoic horizons and a better constrained
kinetics for nitrogen and methane generation at very high levels of maturation
(corresponding to > 3% vitrinite reflectance). The general pattern of the ac-
cumulation and distribution of nitrogen-rich and nitrogen-lean gases in the
Northwest German Basin, as shown in Fig. 7.54, is, however, well explained by
the above described modelling of gas generation and migration.
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Outlook
inertinite 285, 288, 293, 312, 317, 324 kerogen structure 183, 185, 186, 356
inertinite ratio 288 representativity of pyrolysis products (see
infrared spectrometry 181, 185, 248 also pyrolysis) 356
initial porosities 28 Kimmeridge Clay 186, 187,207,286,305,323,
initial saturation values 479 343, 368, 370, 379, 439, 458
interfacial tension 480 kinetics of geochemical reactions 207,212
interglacial stages 279 models 53, 240, 241
inverse modeling 5, 94 parameters 203, 208, 234, 249
Irati Formation 305 Kreyenhagen Formation 136
iron availability 306, 312
iron sulfides 303 La Luna Formation 444
isochemical process 46 lacustrine oil shales 310-312
isomer distribution 189 lacustrine source rocks (see also source
isoprenoid hydrocarbon (see also rocks) 245, 310, 323, 380
hydrocarbons) 187, 362 Laney Shale 246, 380
isothermal kinetics 238 lateral heat conduction 93
isotopic effect 183 Lathrop Formation 136
Italy, source rocks 306, 387 layers, definition of 18
light hydrocarbons (see also
Jambusar Formation 130 hydrocarbons) 174, 189, 342-346
Java Sea 202,317 lignin 182, 186, 317
Jhagadia Formation 130 liptinite 176-180,288,317,324
lithofacies and lithology 19, 416
Kalol Formation 131 basin modeling 19
Kand Formation 132 parameters 468
Kap Stewart Formation 186, 188 variation 416
Kathana Formation 131 lithosphere 9, 86
Kerguelen-Heard plateau 285 stretching 86
kerogen 181, 182, 232, 256, 348, 352, 354, 356, thinning 86
361, 364 live carbon 366
aliphatic 362 live oil 431
alkylcycloalkyl moieties 364 Lodo Formation 136
aromaticity 356 Los Angeles Basin 321
average molecular structural models 352 Lower Saxony Basin 60, 117, 120,212, 242
chemical structure 181, 182 Luman Tongue 246, 380
composition and structure 349
conversion 172 maceral (see coal maceral)
cracking 172, 173 Madagascar coals 317
decomposition 371-374 magmatic activity 82, 120, 140, 146, 148, 150
elemental composition 347 Mahakam Delta 187,201,203, 207, 314, 352,
ester-bound moieties 361 368,437
ether-bound moieties 361 Malacca Strait 462
inert 453 mangroves 307
kinetic aspects 232, 240, 256 Marl Slate 206
molecular typing 348 mass balance model 184, 365, 383, 454, 456
phenolic moieties 364 molecular composition 456
polymethylene moieties 361 PEE value 454
structural moieties 354 petroleum fractions 452
sulfur rich 387 PGI value 454
thermal stability 361 maturation 171, 172, 175-180,233,247,365
types 184, 345, 347, 362 cracking versus condensation reactions
kerogen formation 349-351, 368 365
esterification 350 indicators 210
lignocellulosic degradation 351 kinetic aspects 233, 247
neocondensation 351 maturity 175, 178
selective preservation 349, 450 of bitumen 174
sulfur incorporation 368 of crude oils 174, 189, 198-203
530 Subject Index
salt 324 source rocks 52, 176, 245, 250, 256, 273, 289,
diapir 92, 93, III 305, 342, 343, 345, 348, 359, 365, 366, 368,
dome 49,160 369, 376, 379, 380, 382, 387, 4ll, 423, 427,
movement 49 449
tectonics 486 Alaska 342, 345
thermal conductivity 99 Austria 494
San Andreas transform fault 136 Brae Field area 343
San Joaquin Basin 136,449 California 52, 369, 449
sapropelic coals 314 Canada 174, 190, 200, 204, 365
sea bottom temperature 25-27, 135 China 323
seagrass 307 Colorado 52
secondary migration 340,405,409,461-464 Dampier Sub-basin 343
efficiency 461 deposition 273
flux rates 409 Douala Basin 343
limitations 409 Eastern Alps 380
migration distance 461 France 52, 359, 379
migration losses 461 Germany 379
modeling 476 high permeability domain (see also
path length 409 permeability) 427
residual saturation 461 Indonesia 348
second-order reaction 236 Iowa 359
sediment accumulation rates 20, 292 Italy 387
sediment/water interface temperature 25, 88, Java 359, 382
104 Jordan 387
sedimentary basins 73, 195, 212 Kalimantan 369
geothermal history 73, 195,212 Kansas 379
sedimentation rate 20,22, 96, 97, 106,278,282, low permeability domain (see also
288, 289, 290, 308, 309, 481 permeability) 423
seismic, basin modeling input 18 Michigan Basin 359
selective preservation, kerogen formation (see Middle East 342
also kerogen) 349, 350 Monterey 245
semiempirical quantum mechanical North Sea 360, 361, 379
methods 208 northern Europe 342
sensitivity analysis 58, 95, 499 Norway 124,343,439
separate phase flow 475, 476 occurrence 318
fractures 475 Oklahoma 359, 379
pore system 475 potential 173
sequence stratigraphy (see also thickness 323
stratigraphy) 18 Turkey 142
shallow marine source rocks (see also source Utah 359
rocks) 298, 306 Venezuela 387
Sierra Nevada magmatic arc 139 volume 323
siliciclastic source rocks (see also source Williston Basin 365
rocks) 321 South Viking Graben 439
silled basins 288, 290, 291 specific heat 75, 81
Si0 2 -Na-K-Ca thermometer 93 mica schist 82
siton concept 209, 210 phyllite 82
Smackover Formation 214, 306,444,445 Spitsbergen Island 438
smectite/illite transformation 57, 213 sporinite 179
solid bitumen 179 St. Margarita Formation 136
solid-state I3C nuclear magnetic resonance stability of oil 232, 263
spectrometry 182 StaBfurt-Karbonat 323
C,s+-soluble organic matter 174,175,189,190, sterane 191-199,2ll-213
199 aromatization 198, 212, 213
solution gas-oil ratios (see gas-oil ratio) destruction 194
solution seams 306, 418, 445, 458 formation 194
Songliao Basin 323 functionalized precursors 194
534 Subject Index